Polyelectrolyte Complexes

ABSTRACT

The present invention relates to aqueous compositions of associative polyelectrolyte complexes (PECs), optionally containing surfactants, biocidal agents and/or oxidants, which can provide surface protection to treated articles including reduced soiling tendency, reduced cleaning effort and improved soil repellancy, as well as providing bacteriostatic properties to treated surfaces that thereby gain resistance to water, environmental exposure and microbial challenge. Treatment means and compositions are provided that employ associative polyelectrolyte complexes formed by combining a water soluble cationic first polyelectrolyte with a water soluble second polyelectrolyte bearing groups of opposite charge to the first polyelectrolyte under suitable mixing conditions where the one polyelectrolyte present in molar excess is added in the form of a first aqueous solution during a mixing step to a second aqueous solution comprising the oppositely charged polyelectrolyte present in molar deficiency. Also provided are means to form stable associative polyelectrolyte complexes in aqueous solutions having R values from about 0.10 to 20, including near stoichiometric R values approaching 1, being the ratio of charged groups present on the component polyelectrolytes employed.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to aqueous compositions of associativepolyelectrolyte complexes (PECs) which can provide surface protection totreated articles including reduced soiling tendency, reduced cleaningeffort and improved soil repellancy, as well as providing bacteriostaticproperties to treated surfaces that thereby gain resistance to water,environmental exposure and microbial challenge.

2. Description of the Prior Art

Consumers are dissatisfied with their ability to prevent water andsoils, such as water spots, soap scum, toothpaste, scale, greasy soils,brake dust, grime, rust, and toilet ring, from soiling and building upon household surfaces and other exposed materials. It would be desirableto have treatment means that would easily modify or enhance the surfaceprotective properties of a wide variety of materials to retain and/ormaintain their “like new” appearance and/or clean state and/ordisinfected state for longer periods of time, particularly when exposedto water, soil and microbial challenge. It would further be desirable tohave a treatment means compatible with cleaning aids, so that cleaningand treatment of soiled surfaces could be done either in conjunction orsimultaneously with the treatment means providing enhanced protectionincluding extended antimicrobial activity.

Consumers also desire cleaners and treatments that are convenient to useor that reduce cleaning effort (less surface scrubbing or buffing)during the initial cleaning or treatment, and which provide the benefitof reduced effort or increased speed of subsequent cleaning ortreatment. Products used by professionals, such as janitorial servicesor automobile detailers, that provide reduced cleaning or treatmenttimes are likewise of considerable value in reducing labor costs.

However, many commercial disinfectants employing the use of typicalquaternary ammonium biocides deposited on surfaces to reduce microbialloads tend to leave the treated surfaces that are sticky to the touchand which attract dust and detritus leading to unsightly surfacesrequiring frequent cleaning and reapplication to remain effective. Thereis a need for treatment compositions that provide stable, but thin andinvisible layers or particles on treated surfaces with enhanced surfaceprotective properties, such as reduced adhesion of soil, biological andenvironmental contaminants, or the ability to kill germs that aredeposited onto the surfaces in a variety of ways, including airbornecontaminants, food preparation, direct epidermal contact with humans oranimals, and exposure to bodily fluids. There is a need for compositionsthat can also be employed to simultaneously clean and treat the surfacesso that separate cleaning and treatment steps are not required.

It is therefore an object of the present invention to providecompositions containing associative polyelectrolyte complexes capable oftreating the surfaces of articles that overcome the disadvantages andshortcomings associated with prior art compositions. It is a furtherobject of the present invention to provide compositions and means forthe deposition of associative polyelectrolyte complexes (PECs) which canform densely packed uniform nanometer scale structures on treatedsurfaces when applied in the form of an aqueous treatment composition.

It is another object of the present invention to provide aqueoustreatment compositions of associative polyelectrolyte complexes combinedwith additional cleaning adjuncts and/or biocides useful to effect thetreatment of articles to provide treated surfaces having surfaceprotection benefits such as reduced soiling tendency, reduced cleaningeffort and improved soil repellancy, as well as to providebacteriostatic properties to treated surfaces that have good resistanceto water and environmental exposure.

SUMMARY OF THE INVENTION

In accordance with the above objects and those that will be mentionedand will become apparent below, one aspect of the present invention is atreatment composition and a method of forming a treated article,involving the steps of (a) applying a treatment composition to at leastone surface of an article comprising a suitable substrate material; (b)allowing said treatment composition to deposit at least one layercomprising a plurality of associative polyelectrolyte complexes on saidsurface; and (c) removing said treatment composition from said surfaceby means selected from allowing the surface to drain, allowing thesurface to dry, wiping the surface with a wiping implement, rinsing thesurface with water, and combinations thereof; wherein said treatmentcomposition comprises: (i) an aqueous composition comprising at leastone associative polyelectrolyte complex formed by combining a watersoluble cationic first polyelectrolyte; and a water soluble secondpolyelectrolyte bearing groups of opposite charge to said firstpolyelectrolyte; wherein the one polyelectrolyte present in molar excessis added in the form of a first aqueous solution during a mixing step toa second aqueous solution comprising the oppositely chargedpolyelectrolyte present in molar deficiency; wherein R, the molar ratioof charged groups present on said first polyelectrolyte to oppositelycharged groups present on said second polyelectrolyte is between 0.10 to20; wherein said treatment composition further comprises: (ii) abuffering agent; (iii) optionally, a surfactant; (iv) optionally, abiocidal agent; and (v) optionally, an oxidant.

In another aspect of the present invention is a method of forming atleast one associative polyelectrolyte complex by means of a mixing stepthat is accomplished without high shear mixing, including, but notlimited to means of low energy mixing selected from liquid-to-liquidaddition, stirring, static mixing, paddle mixing, low-shear mixing, andcombinations thereof; wherein said low energy mixing is accomplished attemperatures between 10 to 45° C. In yet another aspect of the presentinvention, the method of forming at least one associativepolyelectrolyte complex is done at a concentration of less than or equalto about 100 millimolar with respect to the total concentration ofcharged associating groups present on the polyelectrolytes making up aplurality of associative polyelectrolyte complexes.

In a further aspect of the present invention is a method of forming aplurality of associative polyelectrolyte complexes having an averageaggregate size in solution of less than about 500 nanometers, oralternatively having an average R_(G) and average R_(H) value insolution of between about 20 nanometers to about 300 nanometers.

In one aspect of the present invention is a method of adding asurfactant to a treatment composition after formation of at least oneassociative polyelectrolyte complex in the treatment composition;wherein the surfactant is selected from the group consisting of watersoluble and/or water dispersible anionic, cationic, zwitterionic,nonionic or amphoteric surfactants. In another aspect of the presentinvention is a method of adding either a biocide or an oxidant, or acombination thereof, to a treatment composition containing at least oneassociative polyelectrolyte complex to provide a treatment compositioncapable of deodorizing, sanitizing and/or disinfecting the surface of anarticle treated with said treatment composition containing the biocideor the oxidant; and optionally a method whereby the surface of thearticle is provided with an extended biocidal or oxidizing effect for aprolonged time after said treatment to provide at least one of adeodorizing, sanitizing and/or disinfecting benefit when exposed to afurther source of microbial contaminants.

In a further aspect of the present invention, the method of forming atreated article involves a second treatment step comprising the step ofapplying to the surface of said article a disinfecting compositioncomprising a biocidal agent and optionally a cleaning adjunct; wherein apreformed layer of a plurality of associative polyelectrolyte complexeson said surface of said treated article thereby incorporates asufficient amount of the biocidal agent present in the disinfectingcomposition so as to provide an effective amount of the biocidal agenton the surface during the second treatment step.

In another aspect of the present invention is a treatment compositionand method of forming a treated article, wherein the surface of thetreated article bears a plurality of associative polyelectrolytecomplexes in the form of a layer which is non-permanent, invisible tothe unaided human eye, capable of sequestering moisture from theatmosphere, and which is less than about 500 nanometers in thickness.

In yet another aspect of the present invention, the associativepolyelectrolyte complexes are made by combining a cationic firstpolyelectrolyte and an oppositely charged second polyelectrolyte thatare not selected from the group consisting of synthetic block copolymer,polymer fluorosurfactant derived from polymerization of a fluorinatedoxetane, cross-linked polyacrylic acid, anionic complexing agent with abulky molecule having an anionic group, silicone polymer, anionic latex,polyacrylate with an average molecular weight below about 10,000Daltons, anionic polysaccharide containing glucoronic acid,N-acylchitosan with an C1-12 alkyl group, and a combination of chitosanand copolymers of acrylate and styrene monomers, and/or styrenederivatives, and/or combinations thereof.

In an aspect of the present invention, the first polyelectrolyte and thesecond polyelectrolyte are polymers that are completely soluble in waterat a level of at least 10 g in 100 ml of water at a temperature of 25°C. In one aspect of the present invention, the associativepolyelectrolyte complexes are formed using a first and secondpolyelectrolyte that are selected from the group consisting of naturaland/or naturally-derived polymers.

In a further aspect of the present invention, an aqueous treatmentcomposition for treating the surface of an article is provided in whichthe treatment composition comprises (i) an aqueous compositioncomprising at least one associative polyelectrolyte complex formed bycombining a water soluble cationic first polyelectrolyte; and a watersoluble second polyelectrolyte bearing groups of opposite charge to saidfirst polyelectrolyte; wherein the one polyelectrolyte present in molarexcess is added in the form of a first aqueous solution during a mixingstep to a second aqueous solution comprising the oppositely chargedpolyelectrolyte present in molar deficiency; wherein R, the molar ratioof charged groups present on said first polyelectrolyte to oppositelycharged groups present on said second polyelectrolyte is between 0.10 to10; wherein the treatment composition further comprises: (ii) abuffering agent; (iii) a surfactant; (iv) optionally, a biocidal agent;and (v) optionally, an oxidant; wherein said cationic firstpolyelectrolyte and said second polyelectrolyte are not synthetic blockcopolymers; and wherein said mixing step is accomplished without highshear mixing.

Further features and advantages of the present invention will becomeapparent to those of ordinary skill in the art in view of the detaileddescription of preferred embodiments below, when considered togetherwith the attached claims.

DETAILED DESCRIPTION OF THE INVENTION

Before describing the present invention in detail, it is to beunderstood that this invention is not limited to particularlyexemplified systems or process parameters that may, of course, vary. Itis also to be understood that the terminology used herein is for thepurpose of describing particular embodiments of the invention only, andis not intended to limit the scope of the invention in any manner.

All publications, patents and patent applications cited herein, whethersupra or infra, are hereby incorporated by reference in their entiretyto the same extent as if each individual publication, patent or patentapplication was specifically and individually indicated to beincorporated by reference.

In the instant application, effective amounts are generally thoseamounts listed as the ranges or levels of ingredients in thedescriptions, which follow hereto. Unless otherwise stated, amountslisted in percentage (“%'s”) are in weight percent (wt %), as based on100% active of that particular component or ingredient present in theindicated formulation or composition.

As used herein, the term “polymer” and “polyelectrolyte” generallyincludes, but is not limited to, homopolymers, copolymers, such as forexample, graft, random and alternating copolymers, terpolymers, etc. andblends and modifications thereof. Furthermore, unless otherwisespecifically limited, the term “polymer” and “polyelectrolyte” shallinclude all possible geometrical configurations of the molecule. Theseconfigurations include, but are not limited to isotactic, syndiotacticand random symmetries. In general, the term “polyelectrolyte”, as usedherein, means and is meant to mean a polymer having at least onepermanent charge, of either an anionic or cationic nature, whendissolved in an aqueous solution. As used herein, the term“polyelectrolyte” also means and is meant to mean a polymer capable offorming a charge, of either an anionic or cationic nature, whendissolved in an aqueous solution whose pH has been adjusted by somemeans including the addition of an acid, a base or suitable bufferingagent, so as to form a net anionic or cationic charge on the polymer inwater.

Molecular weights are generally expressed in terms of the number ofmoles per gram of the compound (MW) and in the case of polymers andpolyelectrolytes are generally expressed in terms of an averagemolecular weight with respect to the plurality of individual polymerspresent within a polymer solution expressed as Daltons (Da).

The term “water soluble” as used herein, means and is meant to mean andinclude materials, particularly the polyelectrolytes of the presentinvention, which are sufficiently soluble or dispersible in water tocreate an optically clear, non-separating and non-precipitating aqueoussolution when present in water at a level of at least about 10 g in 100ml of water at room temperature (25° C.), alternatively at least about20 g in 100 ml of water, or yet alternatively at least about 25 g in 100ml of water at room temperature.

The term “comprising”, which is synonymous with “including,”“containing,” or “characterized by,” is inclusive or open-ended and doesnot exclude additional, unrecited elements or method steps. See MPEP2111.03. See, e.g., Mars Inc. v. H.J. Heinz Co., 377 F.3d 1369, 1376, 71USPQ2d 1837, 1843 (Fed. Cir. 2004) (“like the term ‘comprising,’ theterms ‘containing’ and ‘mixture’ are open-ended.”). Invitrogen Corp. v.Biocrest Mfg., L.P., 327 F.3d 1364, 1368, 66 USPQ2d 1631, 1634 (Fed.Cir. 2003) (“The transition ‘comprising’ in a method claim indicatesthat the claim is open-ended and allows for additional steps.”);Genentech, Inc. v. Chiron Corp., 112 F.3d 495, 501, 42 USPQ2d 1608, 1613(Fed. Cir. 1997) See MPEP 2111.03. (“Comprising” is a term of art usedin claim language which means that the named elements are essential, butother elements may be added and still form a construct within the scopeof the claim.); Moleculon Research Corp. v. CBS, Inc., 793 F.2d 1261,229 USPQ 805 (Fed. Cir. 1986); In re Baxter, 656 F.2d 679, 686, 210 USPQ795, 803 (CCPA 1981); Ex parte Davis, 80 USPQ 448, 450 (Bd. App. 1948).See MPEP 2111.03.

The term “consisting essentially of” as used herein, limits the scope ofa claim to the specified materials or steps “and those that do notmaterially affect the basic and novel characteristic(s)” of the claimedinvention. In re Herz, 537 F.2d 549, 551-52, 190 USPQ 461, 463 (CCPA1976) (emphasis in original). See MPEP 2111.03.

The term “consisting of” as used herein, excludes any element, step, oringredient not specified in the claim. In re Gray 53 F.2d 520, 11 USPQ255 (CCPA 1931); Ex Parte Davis, 80 USPQ 448, 450 (Bd. App. 1948). SeeMPEP 2111.03.

DESCRIPTION OF FIGURES

FIG. 1 illustrates some examples of FT-IR spectra of adsorbed layers ofthe associative polyelectrolyte complexes (PECs) formed on a Ge(germanium) surface exposed 5 minute to an associative PECs formulationsof 1.3 mM total poly(acrylic acid) (PAA) and chitosan. and 0.7 wt %citric acid followed by 50 water rinses and dry nitrogen purge. R valueindicated of separate treatment systems. Acid carbonyl band labeled as“Acid C═O, PAA” and C—O stretching band labeled as “C—O band, chitosan”.

FIG. 2 shows the spectra of the clean IRE surface under the dry nitrogenpurge and in air. H—O—H stretching band of liquid water is 3600 and 3000wavenumber (cm⁻¹). Also shown is a spectrum of a associative PEC layer,labeled “R=1.0, Under Purge”, obtained under dry nitrogen purge on thesame Ge surface after exposing the IRE to a Chitosan/PAA PEC solutionwith R=1.0, followed by 50 rinses. Also shown is the spectrum of thesame associative PEC layer in air, immediately after removal of the drynitrogen purge, labeled “R=1.0, In Air”.

FIG. 3 shows atomic force microscopic images of Chitosan/PAA PECs(R=0.25) on a glass surface treated with formulation CPAA1. Top row (Aand B) views are topographic images, while the bottom row (C and D) arephase images. Dimension of area images (A, C) is 500 by 500 nanometers,and 1.0 by 1.0 micrometers for images (B, D).

FIG. 4 shows atomic force microscopic images of Chitosan/PAA PECs(R=0.25) on a glass surface treated with formulation CPAAG1. Top row (Aand B) views are topographic images, while the bottom row (C and D) arephase images. Dimensions same as FIG. 3.

FIG. 5A shows a secondary electron image of a layer formed on glassthrough exposure to formulation CPAG1. The corresponding FIG. 5B showsthe elemental composition with characteristic X-ray emission spectrum inKeV of species present at the “+” spot sampled indicated and labeled as“Spectrum 40”.

FIG. 6A shows another electron image of an associative PEC particle inthe same layer prepared in Example 18. The corresponding FIG. 6B showsthe elemental composition with characteristic X-ray emission spectrum inKeV of species present at the “+” spot sampled indicated and labeled as“Spectrum 1”.

ASSOCIATIVE POLYELECTROLYTE COMPLEXES

The associative polyelectrolyte complexes (PECs) of the presentinvention have been found to exhibit surprisingly rapid adsorption ontoa wide variety of surfaces, even in the presence of other surface-activeagents commonly employed in cleaning and treatment formulations, toyield thin, invisible layers on the treated surfaces. The adsorption ofthe associative PECs proceeds, even in the presence of othersurface-active agents.

The associative PECs of the present invention comprise at least twodifferent water-soluble polyelectrolytes, each of which bearselectrostatically charged groups, or groups capable of developing acharge (capable of ionization), in which the overall net charges on thetwo polymers are opposite or are capable of becoming opposite throughmanipulation of the pH of the aqueous phase.

The associative PECs of the present invention are assembled in such away that they have an average aggregate size in solution of less thanabout 500 nm, preferably less than 400 nm, more preferably less than 300nm, even more preferably less than 200 nm, and most preferably less thanabout 100 nm in diameter. The particle size and molecular weights of theassociative PECs can be measured via static light scattering (SLS), asdescribed herein. In the initial absence of any charged surfactantsand/or surface active adjuncts, it has been discovered that stableassociative PECs may be produced by the blending of aqueous stocksolutions of the oppositely charged polymers such that the total polymerconcentration in the mixture is less than 100 mM, preferably less than75 mM, more preferably less than 50 mM, and most preferably less than 10mM, and further providing that a specific mixing order as describedherein below is followed in the preparation of the associative PECs.

The blending of the two polymer stock solutions comprising a firstpolyelectrolyte (Polymer A) and a second polyelectrolyte (Polymer B)bearing oppositely charged groups with respect to the overall charge ofPolymer A, can be accomplished by first diluting a stock solution ofPolymer A in the aqueous medium in a tank, and then adding, with simplelow-shear agitation appropriate for the tank size, a stock solution ofPolymer B until the total polymer concentration reaches the desiredfinal concentration. It is preferred to add the stock solution of thepolyelectrolyte which will be in molar excess to an appropriatelydiluted stock solution of the oppositely charged polyelectrolyte whichwill be in molar deficiency in the final solution.

The blending or mixing step may readily be accomplished by means of lowenergy mixing selected from liquid-to-liquid addition, stirring, staticmixing, paddle mixing, low shear mixing, and combinations thereof.Further, the blending or mixing step does not require the use of hightemperatures to improve the solubility of the polyelectrolytes and canreadily be accomplished at most ambient temperatures or with moderateheating, such as for example between temperatures of 10 to 45° C., oralternatively between temperatures of 10 to 35° C., or between 15 to 35°C. or between 15 to 25° C., or between 20 to 30° C.

Surprisingly, since macroscopic solids and gels do not form under theseconditions, high shear or high energy mixing is not required to form theassociative PECs, even for compositions in which there are equal numbersof oppositely charged groups introduced into the aqueous solution, i.e.,even for compositions reaching values of R, as defined below, equal to1.0.

A convenient way to express the composition of the associative PECs isto calculate the ratio of the moles or number of cationic charges tocorresponding moles or number of anionic charges present in thesolution, based on the relative amounts of the polymers added to thebulk solution. Herein below, the parameter “R” is used to denote themolar ratio of cationic (or potentially cationic) groups to that ofanionic (or potentially anionic) groups of the two respectivepolyelectrolytes comprising the associative PECs of the presentinvention., where accordingly:

R=Q ⁺ /Q ⁻

where Q⁺ is the number or moles of cationic charges, Q⁻ is the number ormoles of anionic charges; wherein

Q ⁺=(C _(cationic))*(F _(cationic))*(Q _(cationic))/(M _(cationic))

where C_(cationic) is the concentration of cationic polymer in wt %,F_(cationic) is the weight fraction cationic monomer in total cationicpolymer weight, thus being between 0 and 1, Q_(cationic) is the numberof charges per cationic monomer unit, M_(cationic) is the molecularweight of the monomer unit in polymerized form; and correspondingly:

Q ⁻=(C _(anionic))*(F _(anionic))*(Q _(anionic))/(M _(anionic))

where C_(anionic) is the concentration of anionic polymer in wt %,F_(anionic) is the weight fraction anionic monomer in total anionicpolymer weight, thus being between 0 and 1, Q_(anionic) is the number ofcharges per anionic monomer unit, and M_(anionic) is the molecularweight of the monomer unit in polymerized form.

Polyelectrolytes Suitable for Associative PECs Formulations NaturalCationic Polymers

Any natural cationic polymer may be employed. Chitosan is a preferrednatural polymer, but also acceptable in addition to the naturalpolysaccharide obtained by deacetylation of chitin (from marine source)or by direct isolation from fungi, are those synthetically producedβ-1,4-poly-D-glucosamines and derivatives thereof that are isomers orstructurally similar to natural chitosan. The chitosan polymers of theinvention can have substantially protonated glucosamine monomeric units,improving polymer water solubility, for example, N-hydroxybutylchitosans described in U.S. Pat. No. 4,931,271 to Lang et al. andchitosan pyrithione derivatives described in U.S. Pat. No. 4,957,908 toNelson. Additional polysaccharides suitable for use in the compositionaccording to the invention include, but are not limited to, cationicguar, hydroxypropyl guar and starch bearing cationic charges added bychemical quaternization (for example, but not limited to, alkoxylationwith a quaternary epoxide).

When present the natural cationic polymer level in the compositions ofthe present invention is typically from about 0.001 wt % to about 5.0 wt%, or from about 0.01 wt % to about 2.5 wt %, or from about 0.01 wt % toabout 1.0 wt %, or from about 0.1 wt % to about 0.50 wt %.

Synthetic Cationic Polymers

Suitable cationic polymers include homopolymers or copolymers ofmonomers having a permanent cationic charge or monomers capable offorming a cationic charge in solution upon protonation. Examples ofpermanently cationic monomers include, but are not limited to, diallyldimethyl ammonium salts (such as the chloride salt, referred to hereinas DADMAC) quaternary ammonium salts of substituted acrylamide,methacrylamide, acrylate and methacrylate, such astrimethylammoniumethyl methacrylate, trimethylammoniumpropylmethacrylamide, trimethylammoniumethyl methacrylate,trimethylammoniumpropyl acrylamide, 2-vinyl N-alkyl quaternarypyridinium, 4-vinyl N-alkyl quaternary pyridinium,4-vinylbenzyltrialkylammonium, 2-vinyl piperidinium, 4-vinylpiperidinium, 3-alkyl 1-vinyl imidazolium, and the ionene class ofinternal cationic monomers as described by D. R. Berger in CationicSurfactants, Organic Chemistry, edited by J. M. Richmond, Marcel Dekker,New York, 1990, ISBN 0-8247-8381-6, which is incorporated herein byreference The counterion of the cationic co-monomer can be selectedfrom, for example, chloride, bromide, iodide, hydroxide, phosphate,sulfate, hydrosulfate, ethyl sulfate, methyl sulfate, formate, andacetate.

Examples of monomers that are cationic on protonation include, but arenot limited to, acrylamide, N,N-dimethylacrylamide, N,Ndi-isopropylacryalmide, N-vinylimidazole, N-vinylpyrrolidone,ethyleneimine, dimethylaminohydroxypropyl diethylenetriamine,dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide,dimethylaminoethyl acrylate, dimethylaminopropyl acrylamide, 2-vinylpyridine, 4-vinyl pyridine, 2-vinyl piperidine, 4-vinylpiperidine, vinylamine, diallylamine, methyldiallylamine, vinyl oxazolidone; vinylmethyoxazolidone, and vinyl caprolactam.

Monomers that are cationic on protonation typically contain a positivecharge over a portion of the pH range of 2-11. Such suitable monomersare also presented in Water-Soluble Synthetic Polymers: Properties andBehavior, Volume II, by P. Molyneux, CRC Press, Boca Raton, 1983, ISBN0-8493-6136. Additional monomers can be found in the InternationalCosmetic Ingredient Dictionary, 5th Edition, edited by J. A. Wenningerand G. N. McEwen, The Cosmetic, Toiletry, and Fragrance Association,Washington D.C., 1993, ISBN 1-882621-06-9. A third source of suchmonomers can be found in Encyclopedia of Polymers and Thickeners forCosmetics, by R. Y. Lochhead and W. R. Fron, Cosmetics & Toiletries,vol. 108, May 1993, pp 95-135. All three references are herebyincorporated herein in their entirety.

Cationic polymers may also include other monomers, for example monomershaving an uncharged hydrophilic or hydrophobic group. Suitablecopolymers contain acrylamide, methacrylamide and substitutedacrylamides and methacrylamides, acrylic and methacrylic acid and estersthereof. Suitable synthetic methods for these copolymers are described,for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, Volume1, Fourth Ed., John Wiley & Sons.

The cationic polymer level in the compositions of the present inventionis typically from about 0.001 wt % to about 5.0 wt %, or from about 0.01wt % to about 2.5 wt %, or from about 0.01 wt % to about 1.0 wt %, orfrom about 0.1 wt % to about 0.50 wt %.

Anionic Polymers

Suitable anionic polymers include, but are not limited to,polycarboxylate polymers and copolymers of acrylic acid and maleicanhydride or alkali metal salts thereof, such as the sodium andpotassium salts. Suitable are copolymers of acrylic acid or methacrylicacid with vinyl ethers, such as, for example, vinyl methyl ether, vinylesters, ethylene, propylene and styrene. Also suitable are polymerscontaining monomers capable of taking on an anionic charge in aqueoussolutions when dissolved in water that has been adjusted to anappropriate pH using an acid, a base, a buffer or combination thereof.Examples include, but are not limited to, acrylic acid, maleic acid,methacrylic acid, ethacrylic acid, dimethylacrylic acid, maleicanhydride, succinic anhydride, vinylsulfonate, cyanoacrylic acid,methylenemalonic acid, vinylacetic acid, allylacetic acid,ethylidineacetic acid, propylidineacetic acid, crotonic acid, fumaricacid, itaconic acid, sorbic acid, angelic acid, cinnamic acid,styrylacrylic acid, citraconic acid, glutaconic acid, aconitic acid,phenylacrylic acid, acryloxypropionic acid, citraconic acid,vinylbenzoic acid, N-vinylsuccinamidic acid, mesaconic acid,methacroylalanine, acryloylhydroxyglycine, sulfoethyl methacrylate,sulfopropyl acrylate, and sulfoethyl acrylate. Suitable acid monomersalso include styrenesulfonic acid, acrylamide methyl propane sulfonicacid, 2-methacryloyloxy-methane-1-sulfonic acid,3-methacryloyloxy-propane-1-sulfonic acid,3-(vinyloxy)-propane-1-sulfonic acid, ethylenesulfonic acid, vinylsulfuric acid, 4-vinylphenyl sulfuric acid, ethylene phosphonic acid andvinyl phosphoric acid. Examples of commercially available products areSokalan CP5® and PA30® from BASF, Alcosperse 175® or 177® from Alco andLMW 45N® and SPO2N® from Norsohaas. Also suitable are natural anionicpolymers, including but not limited to saccharinic gums such asalginates, xanthates, pectins, carrageenans, guar, carboxymethylcellulose, and scleroglucans.

The anionic polymer level in the compositions of the present inventionis typically from about 0.001 wt % to about 5.0 wt %, or from about 0.01wt % to about 2.5 wt %, or from about 0.01 wt % to about 1.0 wt %, orfrom about 0.1 wt % to about 0.50 wt %.

Buffer/Electrolyte

Buffers and electrolytes “screen” the interactions between the polymersof the associative PECS of the present invention, and thus may be usedto modify phase behavior, such as preparing formulations “close” to acoacervate phase boundary, which is useful because the complexes becomesufficiently large (up to about 500 nm diameter) or high enough in totalmolecular weight to exhibit enhanced adsorption onto surfaces. Anysuitable electrolyte salt known in the art may be used to control ionicstrength and/or pH of the final formulations. When used herein thebuffer or electrolyte salt is preferably present at a concentration offrom about 0.001 wt % to about 5 wt %, more preferably 0.05 wt % toabout 1 wt %, even more preferably from about 0.05 wt % to about 0.5 wt%, and most preferably 0.1 wt % to about 0.5 wt %.

Antimicrobial Agents

The compositions of the present invention can also, optionally, containantimicrobial agents. Such antimicrobial agents can include, but are notlimited to, alcohols, chlorinated hydrocarbons, organometallics,halogen-releasing compounds, metallic salts, pine oil, organic sulfurcompounds, iodine compounds, silver nitrate, quaternary ammoniumcompounds (quats), chlorhexidine salts, and/or phenolics. Antimicrobialagents suitable for use in the compositions of the present invention aredescribed in U.S. Pat. Nos. 5,686,089; 5,681,802, 5,607,980, 4,714,563;4,163,800; 3,835,057; and 3,152,181, all of which are hereinincorporated by reference in their entirety. Also useful asantimicrobial agents are the so-called “natural” antibacterial actives,referred to as natural essential oils. These actives derive their namesfrom their natural occurrence in plants. Suitable antimicrobial agentsinclude alkyl alpha-hydroxyacids, aralkyl and aryl alpha-hydroxyacids,polyhydroxy alpha-hydroxyacids, polycarboxylic alpha-hydroxyacids,alpha-hydroxyacid related compounds, alpha-ketoacids and relatedcompounds, and other related compounds including their lactone forms.Preferred antimicrobial agents include, but are not limited to,alcohols, chlorinated hydrocarbons, organometallics, halogen-releasingcompounds, metallic salts, pine oil, organic sulfur compounds, iodine,compounds, antimicrobial metal cations and/or antimicrobial metalcation-releasing compounds, chitosan, quaternary alkyl ammoniumbiocides, phenolics, germicidal oxidants, germicidal essential oils,germicidal botanical extracts, alpha-hydroxycarboxylic acids, andcombinations thereof. When incorporated herein the antimicrobial agentis preferably present at a concentration of from about 0.001 wt % toabout 5 wt %, more preferably 0.05 wt % to about 1 wt %, even morepreferably from about 0.05 wt % to about 0.5 wt %, and most preferably0.1 wt % to about 0.5 wt %.

Surfactants

The compositions of the present invention may contain surfactantsselected from nonionic, anionic, cationic, ampholytic, amphoteric andzwitterionic surfactants and mixtures thereof. A typical listing ofanionic, ampholytic, and zwitterionic classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 to Laughlin andHeuring. A list of suitable cationic surfactants is given in U.S. Pat.No. 4,259,217 to Murphy, which is hereby incorporated by reference. Thesurfactants may be present at a level of from about 0% to 90%, or fromabout 0.001% to 50%, or from about 0.01% to 25% by weight.Alternatively, surfactants may be present at a level of from about 0.1to 10% by weight, or from about 0.1 to 5% by weight, or from about 0.1to 1% by weight.

Solvent

Water may be used as a solvent alone, or a combination with any suitableorganic solvents may be present in the compositions of the presentinvention include, but are not limited to, C₁₋₆ alkanols, C₁₋₆ diols,C₁₋₁₀ alkyl ethers of alkylene glycols, C₃₋₂₄ alkylene glycol ethers,polyalkylene glycols, short chain carboxylic acids, short chain esters,isoparafinic hydrocarbons, mineral spirits, alkylaromatics, terpenes,terpene derivatives, terpenoids, terpenoid derivatives, formaldehyde,and pyrrolidones. Alkanols include, but are not limited to, methanol,ethanol, n-propanol, isopropanol, butanol, pentanol, and hexanol, andisomers thereof. The solvents can be present at a level of from 0.001%to 10%, or from 0.01% to 10%, or from 0.1% to 5% by weight, or from 1%to 2.5% by weight.

Oxidants

The compositions of the present invention can also, optionally, containoxidants and/or bleaching agents. Preferred oxidants include, but arenot limited to, hydrogen peroxide, alkaline metal salts and/or alkalineearth metal salts of hypochlorous acid, hypochlorous acid, solubilizedchlorine, any source of free chlorine, solubilized chlorine dioxide,acidic sodium chlorite, active chlorine generating compounds, activeoxygen generating compounds, chlorine-dioxide generating compounds,solubilized ozone, sodium potassium peroxysulfate, sodium perborate, andcombinations thereof. The oxidant can be present at a level of from0.001% to 10%, or from 0.01% to 10%, or from 0.1% to 5% by weight, orfrom 0.5% to 2.5% by weight.

Additional Ingredients

The compositions of the present invention may optionally contain one ormore of the following adjuncts: stain and soil repellants, lubricants,odor control agents, perfumes, fragrances and fragrance release agents,and bleaching agents. Other adjuncts include, but are not limited to,acids, bases, dyes and/or colorants, solubilizing materials,stabilizers, thickeners, defoamers, hydrotropes, cloud point modifiers,preservatives, and other polymers.

Methods of Use

The compositions of the present invention may be used by distributing,e.g., by placing the aqueous solution into a dispensing means,preferably a spray dispenser and spraying an effective amount onto thedesired surface or article. An effective amount as defined herein meansan amount sufficient to modify the surface of the article to achieve thedesired benefit, for example, but not limited to soil repellency and/ordisinfectancy. Distribution can be achieved by using a spray device,such as a trigger sprayer or aerosol, or by other means including, butnot limited to a roller, a pad, a wipe or wiping implement, sponge, etc.

In another embodiment, a surface, an article or a device may be treatedwith the compositions of the present invention by immersing them orexposing the desired portion of the article or device to be treated to abulk liquid solution containing the inventive associative PECs in theform of a treatment composition. Suitable immersion methods includebaths, dipping tanks, wet padding and wet rolling application meanscommon to the art. Such means are also suitable for forming premoistenedwipes wherein a carrier substrate such as a woven material (cloth,towel, etc) or a non-woven material (paper towel, tissue, toilet tissue,bandage) is dipped or padded with the inventive associative PECs in theform of a treatment composition.

EXAMPLES

The associative PECs of the present invention are very effective forincreasing the hydrophilic character of surfaces because the adsorbedlayer formed from exposing surfaces to the associative PECs takes upwater molecules from the ambient atmosphere. Confirmation of the uptakeof water molecules by the adsorbed layers is possible through the use ofFT-IR (Fourier Transform Infrared) spectroscopy.

The following examples are provided to illustrate embodiments of thepresent invention including compositions, methods of formulationcompositions, methods of use and methods of treating surfaces withformulations containing the novel associative polyelectrolyte complexes(PECs) described and claimed herein.

Example 1 Small Scale Preparation of PAA and Chitosan Stock Solutions

A series of PAA/Chitosan PECs was prepared at several R values viagentle mixing using a magnetic stir bar for 1-2 minutes while stirringthe solution, the minor polymeric component being placed in the vesselfirst as designated in the Table 1A with “1” followed by the majorpolymeric component added to the minor component solution designatedwith a “2” next to the weight used. The orders of addition change, ofcourse, depending on the desired R value. The resulting associative PECsolutions were allowed to stir overnight and yielded clear solutions inall cases.

TABLE 1A Compositions of Chitosan/PAA PECs Total 20 wt % concen- Citrictration Stock A Stock B Acid charged Formulation (mL) (mL) (mL) H₂Ogroups # R (a) (b) (c) (d) (mL) (mM) SCPAA1 0.25 0.4515 (1) 0.7615 (2)0.5524 16.7580 1.29 SCPAA2 0.51 0.7505 (1) 0.6319 (2) 0.4972 16.44921.30 SCPAA3 0.77 0.9731 (1) 0.5419 (2) 0.4370 16.5710 1.29 SCPAA4 1.051.1382 (1) 0.4661 (2) 0.3967 16.5342 1.28 SCPAA5 1.27 1.2580 (2) 0.4238(1) 0.3728 16.4988 1.30 SCPAA6 1.55 1.3408 (2) 0.3714 (1) 0.3502 16.44061.28 SCPAA7 1.78 1.4312 (2) 0.3446 (1) 0.3316 16.4275 1.29 SCPAA8 2.051.5124 (2) 0.3164 (1) 0.3207 16.3751 1.30 SCPAA9 3.15 1.6960 (2) 0.2306(1) 0.2641 16.3056 1.29 SCPAA10 4.05 1.7941 (2) 0.1896 (1) 0.246316.2738 1.29 (a) R = [Cationic amine groups from chitosan]/[Anionic acidgroups from PAA] (b) 0.2 wt % Federal Laboratories chitosan (c)Alcosperse 465 PAA providing 33.1 mM charged acrylate groups (d)Providing total of 0.7 wt % citric acid at a pH of 2.2 in all finalformulations.

Large Scale Preparation of Chitosan/PAA PECs

A series of PAA/Chitosan PECs was prepared at several R values inapproximately 0.7 wt % citric acid at a pH of 2.2 and can be found belowin Table 1B.

TABLE 1B Compositions of Chitosan/PAA PECs Aldrich Alcosperse TotalChitosan 465 PAA 10 wt % concentration R Stock A Stock B Citri Acid H₂Ocharged groups Formulation # (3) (mL) (mL) (mL) (mL) (mM) CPAA 1 0.25 8.2600 (1) 9.4500 (2)  19.8900 263.4200 1.30 CPAA 2 0.50 13.8000 (1)7.91 (2) 17.4400 261.8100 1.30 CPAA 3 0.75 17.7100 (1) 6.78 (2) 15.7500260.6800 1.30 CPAA 4 1.00 20.6500 (1) 5.95 (2) 14.2300 260.0600 1.31CPAA 5 1.26 23.0000 (2) 5.25 (1) 13.3900 259.2200 1.30 CPAA 6 1.4924.6800 (2) 4.74 (1) 12.5300 258.8700 1.30 CPAA 7 1.76 26.2000 (2) 4.28(1) 11.8400 258.4800 1.30 CPAA 8 2.01 27.5100 (2) 3.93 (1) 11.3400258.0500 1.30 CPAA 9 3.00 31.0300 (2) 2.97 (1) 9.7500 257.0800 1.30 CPAA10 4.04 32.9000 (2) 2.34 (1) 8.8200 256.6900 1.30 (1) Minor polymericcomponent (2) Major polymeric component (3) R = [Cationic Amine groupsfrom chitosan]/[Anionic Acid groups from PAA]

FT-IR spectroscopy can be used to characterize extremely thin layers ofmaterials on hard surfaces. It is known in the art that it is convenientto use an optical accessory based on the principle of attenuated totalreflectance (ATR) in such FT-IR work. FT-IR spectroscopy is described inFourier Transform Infrared Spectrometry, by P. R. Griffiths. ATR opticalaccessories are described in Internal Reflection Spectroscopy, by N. J.Harrick, Interscience Publishers, 1967, and Internal ReflectionSpectroscopy Review and Supplement, by F. M. Mirabella Jr., N. J.Harrick, Editor, Harrick Scientific Corporation, 88 Broadway, Box 1288,Ossining, N.Y. 10562. The optical accessory used in the measurementsdescribed herein was a “Horizon”, available from Harrick ScientificCorporation, equipped with an internal reflection element (IRE)constructed from Ge.

The hydrophilic modification of a surface by some of the associativePECs described in Tables 1A and 1B were investigated with FT-IRspectroscopy using a clean Ge IRE for which a background absorbancespectrum under dry nitrogen purge was first recorded, as well as a“blank” for the particular IRE in its clean state in contact with theambient atmosphere with the current humidity. The intensity of theabsorbance band at 3365 cm⁻¹, which is due to the H—O—H stretching bandof liquid water in the spectrum recorded, is measured to find therelative amount of water on the IRE surface, recorded in Table 1C belowas the “B” values. The magnitude of the bands in all of the FT-IRspectra in this specification are expressed in milli-Absorbance Units(mAU), which are linearly related to concentration at the IRE surface.

The uptake of water by the extremely thin adsorbed layers is very rapid,and can be readily observed by the changes in the FT-IR spectra obtainedwith and without the dry purge. The difference is directly proportionalto the amount of water uptake achieved by the adsorbed layer and arepresented in Table 1C below as the “A” values. Finally, the increase inthe surface water contents due to the presence of the adsorbedassociative PEC layer is shown below in Table as value “C”, computedfrom “A”-“B”.

TABLE 1C Chitosan/PAA PECS “A” Modified “C” surface “B” Water NumberWater IRE Water uptake in of Uptake Uptake PEC layer Formulation # RRinses (mAU) (mAU) (mAU) CPAA-10 4.04 10 1.453 1.046 0.407 CPAA-10 4.0450 1.417 1.046 0.371 CPAA-4 1.0 10 1.567 1.012 0.555 CPAA-4 1.0 50 1.6591.012 0.647 CPAA-2 0.5 10 1.507 1.127 0.38 CPAA-2 0.5 50 1.602 1.1270.475 CPAA-3 0.76 10 1.749 1.083 0.666 CPAA-3 0.76 50 1.855 1.083 0.772CPAA-8 2.01 10 1.686 1.253 0.433 CPAA-8 2.01 50 1.722 1.253 0.469 CPAA-93.0 10 1.69 1.363 0.327 CPAA-9 3.0 50 1.564 1.363 0.201 CPAA-10 4.04 (1)10 1.997 1.574 0.423 CPAA-10 4.04 (1) 50 2.00 1.574 0.426 CPAA-1 0.25(1) 10 2.104 1.421 0.683 CPAA-1 0.25 (1) 50 2.107 1.421 0.686 CPAA-10.25 (1) 100 1.893 1.421 0.472 (1) Sample measurements obtained after 30minute adsorption time “A” = Difference in absorbance at 3365 cm⁻¹ inAir and under purge. “B” = Difference in absorbance at 3365 cm⁻¹ forcorresponding blank run. “C” = “A” − “B”

Data in Table 1C demonstrates the ability of the associative PECs of thepresent invention to sequester atmospheric moisture when present as adeposited layer on a substrate. The FT-IR spectra of the adsorbed layersformed on the IRE by exposing it to solutions containing associativePECs can also be used to determine the relative amounts of the polymerspresent in a layer.

In all of the FT-IR experiments, use of the specified optical accessoryallows visual inspection of the IRE surface, which permits an assessmentof whether the surface bears a visible residue or not. The associativePECs of the present invention are useful for the modification ofsurfaces without the formation of visible residues, because the adsorbedlayers formed by the associative PECs are so thin (<500 nm), and are notmacroscopic films, as are commonly formed from coatings or polishes, andcannot be seen by the unaided human eye when present on treatedsurfaces.

Example 2

The size of the stable associative PECs, and the composition of the thinadsorbed layers formed by treating surfaces with aqueous solutions ofPECs can be controlled by changing the ratio of the polymers comprisingthe associative PECs, i.e., by changing the R parameter.

The FT-IR spectrum of chitosan, PAA and citric acid all exhibit one ormore unique absorbance bands allowing their presence, as well asrelative amount present on the surface of the IRE to be detected andmonitored in real time.

The data in Table 2 illustrate that the composition of a layer can becontrolled by varying the R parameter of the associative PECs. Sincethere were no added surfactants, the data also illustrate the surprisingactivity of the associative PECs solutions on a solid surface, even inthe absence of a drying step and any “wetting” of the solid surface bysurfactants.

Referring to Table 2, in one experiment with the R=0.25 associative PECsolution, the adsorption time was 5 minutes, and the layer was rinsed 10times, yielding the band intensities listed (sample CPAA1, layeranalysis A being denoted as “CPAA1-A”, for example). A second treatmentof the IRE was then done (exposure #2) with the adsorbed layer in place,followed by 10 and then 50 total rinses. The relatively small increasein the amount of chitosan and PAA caused by the second exposure, seencomparing examples CPAA1-A and CPAA1-B, shows that adsorption onto thesurface was nearly complete in the first 5 minute exposure, i.e. thatthe formation of a layer formed from the associative PEC solutions isdesirably rapid, and that the layer is very substantive, since in thesecond exposure there was no net loss, but in fact a net gain in theamounts of both chitosan and PAA on the surface. The associative PEClayer was also very substantive, as indicated by the relatively smallchange in band intensities caused by additional rinsing (compare CPAA1-Band CPAA1-C). In another experiment with the R=0.25 associative PECsolution, the adsorption time was increased to 30 minutes, but therelative amounts of chitosan and PAA initially adsorbed are very similarto that achieved with two exposures of shorter time, as seen bycomparing CPAA 1-D and CPAA 1-E with CPAA 1-B and CPAA 1-C,respectively. These data show that layer formation from the associativePECs formulations is “self-limiting”, i.e., the average thickness of theadsorbed layers (directly proportional to the absorbance intensities,since the area of the IRE is the same and fixed in all experiments) doesnot grow to macroscopic dimensions which would otherwise become visibleto the eye, instead appearing to be self-limiting and maintaining a filmof less than 500 nm thickness. In addition, 50 additional rinses, for atotal of 100 rinses, was done with the layer formed in the thirdexperiment. The band intensities show only a very slight decrease in theband intensities of both polymers, i.e., the layers are verysubstantive, as seen by comparing CPAA 1-E with CPAA 1-F. After 50rinses, all citric acid was eventually rinsed away, indicating utilityof the PECs films to release actives over time.

Also discovered is that treatment of the surface with associative PECswith R<1, which are relatively rich in PAA, and with R>1, which arerelatively rich in chitosan, both result in layers with more chitosanwith more substantivity than the control solution of chitosan alone,enabling the control of the layer composition by using treatmentsolutions with selected R values. In the absence of the associativePECs, PAA alone does not absorb onto the surface.

The band intensity ratios in Table 2 show that the composition of thelayers provided by the solutions of the associative PECs can becontrolled by changing the R value. As the R value increases, therelative amount of chitosan in the layers also increases. Thus, the bandintensity ratio is found to be 1.1291 for formulation CPAA1-C(R=0.25),and is found to be 3.6038 for formulation CPAA10-B (R=4.0).

TABLE 2 Chitosan/Alcosperse 465 PAA PECs Band Chitosan PAA IntensityAdsorption Number C—O band C═O band Ratio Chitosan Time of absorbanceabsorbance C—O/PAA Formulation # R (min) Rinses (mAU) (mAU) C═O CPAA1 -A 0.25 5 10 2.94 2.567 1.1453 CPAA1 - B 0.25 5 (2) 10 3.45 3.488 0.9891CPAA1 - C 0.25 — 50 3.227 2.858 1.1291 CPAA1 - D 0.25 30  10 3.216 3.3150.9701 CPAA1 - E 0.25 — 50 3.11 2.83 1.0989 CPAA1 - F 0.25 — 100 3.0732.606 1.1792 CPAA2 - A 0.50 5 10 2.819 1.898 1.4852 CPAA2 - B 0.50 — 502.819 1.704 1.6543 CPAA2 - C 0.50 30  10 2.991 2.609 1.1464 CPAA2 - D0.50 — 50 2.881 2.443 1.1793 CPAA3 - A 0.75 5 10 2.847 1.509 1.8867CPAA3 - B 0.75 — 50 2.859 1.378 2.0747 CPAA4 - A 1.0 5 10 2.798 1.3572.0619 CPAA4 - B 1.0 — 50 2.781 1.171 2.3749 CPAA4 - C 1.0 5 10 2.8131.37 2.0533 CPAA4 - D 1.0 — 50 2.77 1.225 2.2612 CPAA5 - A 1.26 5 102.902 1.334 2.1754 CPAA5 - B 1.26 — 50 2.94 1.041 2.8242 CPAA6 - A 1.495 10 2.595 1.122 2.3128 CPAA6 - B 1.49 — 50 2.629 0.976 2.6936 CPAA7 - A1.76 5 10 2.605 1.036 2.5145 CPAA7 - B 1.76 — 50 2.603 0.873 2.9817CPAA8 - A 2.01 5 10 2.595 1.028 2.5243 CPAA8 - B 2.01 — 50 2.564 0.8273.1004 CPAA9 - A 3.0 5 10 2.173 0.739 2.9405 CPAA9 - B 3.0 — 50 2.080.608 3.4211 CPAA10 - A 4.0 5 10 2.278 0.766 2.9739 CPAA10 - B 4.0 — 502.292 0.636 3.6038 C1-A — 5 10 1.812 0.497 3.6459 Chitosan control (1)C1-B — — 50 1.794 0.198 9.0606 Chitosan control (1) (1) Concentration ofchitosan was 1.3 mM (2) Additional exposure time of 5 minutes

Example 3

The associative PECs of the present invention, when made with polymersthat exhibit chemical stability to oxidants such as sodium hypochloriteor hydrogen peroxide, are useful for providing hydrophilic modificationof surfaces through the use of cleaning products familiar to consumers.

Hypochlorite-stable associative PECs can be made from mixtures of thealkali metal salt of poly(acrylic acid) (PAA) and poly(diallyl dimethylammonium chloride) denoted as poly(DADMAC) or simply DADMAC. However,the surface of a Ge IRE suitable for the FT-IR experiments is changed byexposure to sodium hypochlorite, which is a relatively strong oxidant.Thus, the formulations cited in Tables 3.1 and 3.2 below, which are usedto demonstrate associative PEC stability and substantivity, wereformulated using sodium chloride as a substitute for the sodiumhypochlorite. It is believed, without being bound by theory, that thedifference between the chloride and hypochlorite salts is immaterial,both being electrolytes, to the behavior of the associative PECs interms of the delivery of adsorbed layers. Independently, stability ofthe oxidant containing PECs compositions confirmed stability of both thebleach and PEC component polymers after prolonged storage.

TABLE 3.1 DADMAC/PAA PECs Total NaCl concentration PAA DADMAC Surfactant(wt %) charged groups Formulation # (mM) (1) (mM) (2) R (wt %) (3) (4)(mM) Evaluation 3DAD/PAA 2 0.558 0.116 0.207 — 0.1201 0.674 Stable3DAD/PAA 3 0.580 0.225 0.387 — 0.1132 0.804 Stable 3DAD/PAA 4 0.5650.325 0.575 — 0.1145 0.891 Stable 3DAD/PAA 5 0.577 0.424 0.735 — 0.11691.001 Stable 3DAD/PAA 9 0.567 0.859 1.515 — 0.1261 1.426 Stable 3DAD/PAA12 0.549 1.177 2.144 — 0.1257 1.726 Stable 6DAD/PAA 2 0.549 0.108 0.1970.0254 0.1208 0.657 Stable 6DAD/PAA 3 0.530 0.226 0.427 0.0243 0.11160.757 Stable 5DAD/PAA 2 0.541 0.117 0.217 0.0509 0.1522 0.658 Stable5DAD/PAA 4 0.537 0.329 0.612 0.0508 0.1226 0.866 Stable 5DAD/PAA 5 0.5340.449 0.842 0.0494 0.1266 0.983 Stable 5DAD/PAA 8 0.527 0.757 1.4370.0520 0.1229 1.283 Stable 5DAD/PAA 9 0.530 0.855 1.615 0.0505 0.13231.385 Stable 5DAD/PAA 12 0.529 1.161 2.196 0.0504 0.1154 1.690 Stable2DAD/PAA 2 0.603 0.106 0.175 0.3040 0.1365 0.709 Stable 2DAD/PAA 4 0.5710.321 0.562 0.3047 0.1319 0.891 Stable 2DAD/PAA 5 0.569 0.417 0.7320.3046 0.1232 0.986 Stable 2DAD/PAA 8 0.562 0.728 1.296 0.3077 0.15121.289 Stable 2DAD/PAA 10 0.552 0.985 1.784 0.3102 0.1525 1.538 Stable2DAD/PAA 12 0.557 1.182 2.122 0.3065 0.1543 1.740 Stable 7DAD/PAA 20.541 0.120 0.222 0.8964 0.1194 0.661 Stable 7DAD/PAA 4 0.645 0.3260.506 0.8890 0.1154 0.971 Stable 7DAD/PAA 5 0.551 0.435 0.789 0.90100.1143 0.986 Stable 7DAD/PAA 12 0.535 1.161 2.170 0.9017 0.1115 1.697Stable (1) Poly(DADMAC) from Aldrich, batch 02319JC, average MW of 2.5 ×10⁵ Daltons, final dilution to 0.1661 wt % (about 10.3 mM cationicgroups), pH 12 (2) Aquatreat AR-4, 0.0774 wt % (about 10.9 mM anioniccarboxylate groups), pH 12. (3) 20 wt % sodium chloride pH 12.0. (4) 3wt % Amine oxide, Ammonyx LO (Stepan Corp.), pH 12.

TABLE 3.2 DADMAC/PAA PECs Total NaCl concentration PAA DADMAC Surfactant(wt %) charged groups Formulation # (mM) (1) (mM) (2) R (wt %) (3) (4)(mM) Evaluation 8DAD/PAA 2 0.557 0.118 0.211 — 0.1195 0.675 stable8DAD/PAA 3 0.559 0.220 0.394 — 0.1195 0.779 stable 8DAD/PAA 4 0.5530.333 0.602 — 0.1210 0.886 stable 8DAD/PAA 5 0.574 0.429 0.747 — 0.11931.002 stable 8DAD/PAA 6 0.595 0.537 0.904 — 0.1205 1.132 stable 8DAD/PAA11 0.561 1.080 1.926 — 0.1190 1.641 stable 8DAD/PAA 12 0.559 1.160 2.074— 0.1189 1.719 stable 9DAD/PAA 2 0.561 0.218 0.388 0.0235 0.1194 0.779stable 9DAD/PAA 3 0.557 0.105 0.188 0.0236 0.1196 0.662 stable 9DAD/PAA4 0.553 0.218 0.394 0.0231 0.1199 0.771 stable 9DAD/PAA 5 0.595 0.3080.518 0.0232 0.1191 0.903 stable 9DAD/PAA 6 0.576 0.410 0.711 0.02350.1197 0.986 stable 9DAD/PAA 7 0.553 0.527 0.953 0.0237 0.1197 1.080stable 10DAD/PAA 3 0.561 0.211 0.376 0.0494 0.1211 0.772 stable10DAD/PAA 4 0.553 0.321 0.580 0.0485 0.1254 0.874 stable 10DAD/PAA 50.562 0.415 0.738 0.0484 0.1294 0.977 stable 10DAD/PAA 11 0.563 0.9981.772 0.0480 0.1164 1.561 stable 10DAD/PAA 12 0.565 1.124 1.991 0.04830.1175 1.689 stable 11DAD/PAA 2 0.551 0.102 0.186 0.8990 0.1207 0.654stable 11DAD/PAA 3 0.558 0.199 0.357 0.8994 0.1273 0.757 stable11DAD/PAA 4 0.549 0.319 0.581 0.8970 0.1170 0.869 stable 11DAD/PAA 50.547 0.409 0.747 0.9008 0.1207 0.956 stable 11DAD/PAA 6 0.550 0.5190.944 0.9007 0.1205 1.068 stable (1) Poly(DADMAC) from Aldrich,, batch05525PB average MW of 1.0 to 2.0 × 10⁵ Daltons, pH 12, diluted to 0.1701wt % (about 10.56 mM cationic groups). (2) Aquatreat AR-7H poly(acrylicacid) from Alco Chemical, average MW of 8.72 × 10⁵ Daltons, pH 12,diluted to 0.0780 wt % (about 10.99 mM anionic carboxylate groups). (3)20 wt % sodium chloride, pH 12. (4) 3.0 wt % Amine oxide, Ammonyx LO(Stepan Corp)., pH 12.

Table 3.2 evaluates formulations without and with hypochlorite-stablesurfactant with associative PECs made using low molecular weightpoly(DADMAC) and higher molecular weight PAA. The formulations were madein the same way as those described in Table 3.1.

The compositions in Tables 3.1 and 3.2 illustrate that stable DADMAC/PAAassociative PECs can be assembled over a wide range of R values, over awide range of surfactant concentrations useful in the control of thesurface wetting and cleaning properties of the formulations, and in thepresence of significant concentrations of an electrolyte. In contrast tothe known art, when the associative PECs are assembled in the mannerdescribed herein, stable systems can be produced without particularregard to the relative molecular weights of the polymers comprising theassociative PECs. Table 3.3 reports FT-IR band intensities in spectra ofadsorbed layers formed by exposure of Ge IRE to solutions containingassociative PECs described in Table 3.1 for 5 minutes, followed byimmediate rinsing. Spectra were obtained under dry nitrogen purge.

Multiple exposures of the Ge surface were made using the inventivecompositions for 5 minutes, followed by rinsing the surface 20 timeswith water, and then the spectra were recorded. This adsorbed layer wasthen exposed to the indicated associative PEC solution again, followedby rinsing, and a spectrum recorded for “exposure 2”. A third exposurewas done in the same way. The small increase in the amounts of DADMACand PAA caused by the second and third exposures shows that adsorptiononto the surface was nearly complete in the first 5 minute exposure,i.e. that the formation of the adsorbed layers formed from theassociative PEC solutions is fairly rapid, and that while the adsorbedlayers are very substantive, they nevertheless tend to self-equilibrateand maintain a favorably thin invisible layer on a treated surface,rather than building up to undesirable macroscopic (and hence visible)layers

Polymer PAA, which becomes negatively charged at pH 12, as in theexamples in Tables 3.1, 3.2 and 3.3, does not adsorb onto the Gesurface, which is also slightly negatively charged. However, PAA isclearly present in the adsorbed layers when delivered via treatmentusing the inventive associative PEC solutions.

TABLE 3.3 PAA DADMAC Carboxylate CH₃ Treatment (2) Formulation # (mAU)(mAU) R Number of Rinses 3DAD/PAA 4 0.531 0.557 0.5752 20 3DAD/PAA 51.066 0.692 0.7349 20 3DAD/PAA 8 2.702 1.045 1.3072 20 3DAD/PAA 4 0.6860.568 0.5752 20 3DAD/PAA 4 1.045 0.671 0.5752 40 3DAD/PAA 4 1.166 0.7210.5752 60 Control (1) 0.078 0.57 N/A 20 (1) DADMAC polymer only at 10.0mM concentration in sodium chloride solution. (2) Exposed to formulationindicated for 5 minutes with no separate drying step, followed by numberof rinses indicated.

Example 4

The following example demonstrates surface modification using DADMAC/PAAassociative PECs in treatment compositions having a hypochlorite-stablesurfactant. FT-IR was used to determine the formation of adsorbed layersfrom associative PEC solutions containing various amounts of arelatively oxidant-stable surfactant, Ammonyx LO. These illustrativecompositions are suitable as ready-to-use treatment compositions.

TABLE 4.1 PAA DADMAC Carboxylate CH₃ Formulation # (mAU) (mAU) R7DAD/PAA 2 0.295 0.509 0.222 7DAD/PAA 3 0.407 0.474 0.308 7DAD/PAA 40.687 0.582 0.506 7DAD/PAA 5 0.985 0.659 0.789 7DAD/PAA 6 0.085 0.2760.988 7DAD/PAA 7 1.295 0.738 1.191 7DAD/PAA 8 2.753 1.016 1.389 7DAD/PAA9 1.858 0.94 1.597 7DAD/PAA 10 1.99 0.898 1.756 7DAD/PAA 11 1.31 0.8171.974

In Table 4.1, the Ge IRE surface was treated with the indicatedcompositions for 5 minutes, followed by 20 rinses with water without adrying step, the spectra obtained under a dry nitrogen purge. Resultsshow that the adsorbed associative PECs layers are formed rapidly, evenin the absence of a drying step, and even in the presence of surfactant,both PAA and DADMAC being confirmed as present in the adsorbed layers.

TABLE 4.2 PAA Carboxylate DADMAC Formulation # (mAU) CH₃ (mAU) R (1)7DAD/PAA 2 0.562 0.581 0.222 7DAD/PAA 3 0.892 0.596 0.308 7DAD/PAA 42.662 0.985 0.506 7DAD/PAA 5 2.422 0.94 0.789 7DAD/PAA 6 0.178 0.3190.988 7DAD/PAA 7 1.084 0.75 1.191 7DAD/PAA 8 5.089 1.454 1.389 7DAD/PAA9 5.247 1.565 1.597 7DAD/PAA 10 5.441 1.583 1.756 7DAD/PAA 11 3.0341.156 1.974 (1) FT-IR band intensities in the spectra of adsorbed layersformed by drying 10 microliters of formulations containing DADMAC/PAAPECs and 0.89% Ammonyx LO on the IRE surface, followed by 20 rinses withwater. Spectra of layers obtained under dry nitrogen purge.

Table 4.2 represents results of surface modification with DADMAC/PAAPECs utilizing a drying step following treatment. Here results indicatethat, even in the presence of significant amounts of surfactant,substantive adsorbed layers are formed from the formulations containingthe associative PECs, and the total amount of adsorbed polymers isincreased somewhat. Without being bound by theory, it is believed thatthe drying step immediately following treatment enables rearrangement ofthe PECs on the surface, likely resulting in a denser layer and/ordenser array of the associative PECs at the surface.

Several additional DADMAC/PAA PECs were evaluated, reversing therelative molecular weights of the polymers used. The data in Table 4.3show that adsorbed layers from these systems are also produced in thepresence of surfactant and a drying step, despite extensive rinsing withwater. Control of the stability of the associative PECs throughselection of appropriate R values, which controls the composition andsize of the associative PECs, can be achieved with a range of polymersof the same chemical type, but varying in molecular weight.

TABLE 4.3 PAA Carboxylate DADMAC Formulation # (mAU) (1) CH₃ (mAU) (1) R11DAD/PAA 2 0.097 0.258 0.186 11DAD/PAA 3 0.282 0.446 0.357 11DAD/PAA 40.551 0.488 0.581 11DAD/PAA 5 0.853 0.622 0.747 11DAD/PAA 6 2.081 0.7810.943 (1) FT-IR band intensities in the spectra of adsorbed layersformed by drying 10 microliters of formulations containing DADMAC/PAAPECs and 0.89 wt % Ammonyx LO on the IRE surface, followed by 20 rinseswith water. Spectra of layers obtained under dry nitrogen purge. Thesystems were all found to be stable.

Example 5

Results in Table 5 show that the relative amounts of water taken up bythe thin adsorbed layers of DADMAC/PAA PECs from Example 4 followingvarious application, drying and rinsing steps.

TABLE 5 “A” “B” “C” PAA Carboxylate DADMAC Water uptake in Formulation #(mAU) CH₃ (mAU) PEC layer (mAU) (1) R Treatments (2) 7DAD/PAA 5 0.6960.689 0.30 0.789 No dry step Rinsed 7DAD/PAA 5 1.71 0.949 1.16 0.789Dried Rinsed 7DAD/PAA 11 1.244 0.929 0.92 1.974 No dry step Rinsed7DAD/PAA 11 2.735 1.277 2.087 1.974 Dried Rinsed 7DAD/PAA 12 1.327 0.9110.871 2.17 No dry step Rinsed 7DAD/PAA 12 2.955 1.351 2.409 2.17 DriedRinsed (1) “C” = “B” − “A” (2) “No dry step” means 5 minute exposure toformulation containing associative PECs, followed by 20 rinses withwater. “Dried” means 10 microliters of formulation was spread on IRE,allowed to dry, and then rinsed 20 times with water.

Table 5 results demonstrate that more water is taken up at the surfacein the presence of the adsorbed layers, compared to the untreated Gesurface, and that the amount of water present increases as the amount ofassociative PECs (total polymer) on the surface increases. Thus,hydrophilic thin adsorbed layers can be produced from formulationscontaining oxidant-stable associative PECs.

Example 6

The following examples demonstrate hypochlorite stability in treatmentcompositions containing DADMAC/PAA PECs, which all show acceptablestability against precipitation and degradation by the optional bleachcomponent being present.

TABLE 6.1 % of Salt Initial Hypochlorite Sample R Surfactant (wt %)Buffer Hypochlorite Remaining # (1) (wt %) (2) (3) Type (3) (wt %) (4)(5) A1 0.25 0 0.016 Na₂O•SiO₂ 0.020 89 A2 0.50 0 0.016 Na₂O•SiO₂ 0.02072 A3 0.50 0 0.022 K₂CO₃ 0.025 83 A4 0.25 0.005 0.021 K₂CO₃ 0.025 81 A50.50 0.005 0.021 K₂CO₃ 0.025 83 A6 0.05 0.02 0.022 K₂CO₃ 0.027 79 A70.30 0.02 0.021 K₂CO₃ 0.026 76 A8 0.05 0.02 0.41 K₂CO₃ 0.500 88 A9 0.300.02 0.41 K₂CO₃ 0.500 80 A10 0.05 0.02 1.65 K₂CO₃ 2.00 84 A11 0.30 0.021.64 K₂CO₃ 2.00 83 (1) PAA = Aquatreat AR-4 ™, the total combined finalpolymer concentration being 1.5 mM in all formulations. (2) Ammonyx LO ™available from the Stepan Co. (3) Sodium chloride, sodium silicate,sodium hydroxide, potassium carbonate were J. T. Baker reagent grade.(4) Sodium hypochlorite (Clorox ™ Regular Bleach, 6.7-6.9 wt %hypochlorite assayed) (5) After 4 weeks at 120° F. All samples remainedclear and free of precipitates.

Formulations A1 through A3 illustrate useful embodiments of the presentinvention suitable for us as daily after shower treatment compositionsthat provide hydrophilic modification of surfaces via the adsorption ofthe DADMAC/PAA PECs, and daily germ reduction employing relatively lowhypochlorite levels. Formulations A4 and A5 are embodiments useful asready-to-use treatment compositions that provide hydrophilicmodification of hard surfaces, including sink basins, toilet exteriors,floors, and countertops, also providing cleaning due to theincorporation of surfactant, and germ and mildew reduction due to thehypochlorite present. Formulations A6 through A11 further illustrateembodiments stable at higher ionic strengths and elevated surfactantlevels, and demonstrate chemical stability of sodium hypochlorite in thepresence of associative PECs with or without the presence of commonbleach stable surfactants available for commercial usage.

TABLE 6.2 Surfactant Starting % HOOH Sample # R (1) (wt %) (2) HOOH (wt%) remaining (3) B1 20 0.02 1.11 84 B2 3.3 0.02 1.08 85 B3 20 0.10 1.0892 B4 3.3 0.10 1.10 94 B5 20 0.02 2.13 86 B6 3.3 0.02 2.13 87 B7 20 0.12.13 91 B8 3.3 0.1 2.14 93 B9 20 0.02 4.21 85 B10 3.3 0.02 4.19 87 B1120 0.1 4.27 91 B12 3.3 0.1 4.25 92 (1) Total concentration of chargedgroups from polymers 1.5 mM, pH 2-3, stored at 120° F. for 4 weeks. (2)3 wt % final Ammonyx LO surfactant, added after PEC formation, beingcharged at formulation pH. (3) All samples remained clear withoutprecipitate.

Example 7

Formulations shown in Tables 7.1 and 7.2 demonstrate that thin,invisible adsorbed layers can be formed by exposing the surface to bemodified to bleach tolerant formulations of stable associative PECsformed from R values of <1.0 and >1.0. FT-IR band intensities weremeasured in the spectra of adsorbed layers formed by drying 10microliters of formulations shown in Table 7.1 of DADMAC/Alcosperse 747PECs on an Ge IRE surface, followed by 20 rinses with water, followed bydry nitrogen purge.

TABLE 7.1 DADMAC Total Alcosperse Acid group quaternary Ammonyxconcentration 747 DADMAC molarity group molarity NaCl LO charged groupsFormulation # (wt %) (wt %)(1) (mM) (mM) R (wt %) (wt %) (mM), pH 12Comment DAD747 1 0.0096 0.0053 0.55 0.33 0.6 0 0 0.88 Stable ClearDAD747 2 0.0096 0.0177 0.55 1.1 2.0 0 0 1.65 Stable Clear DAD747 30.0096 0.0177 0.55 1.1 2.0 0.22 0.90 1.65 Stable Clear

TABLE 7.2 Alcosperse 747 DADMAC Carboxylate CH₃ Formulation # (mAU)(1,2)(mAU)(2) R DAD747 1 4.154 1.266 0.6 DAD747 2 3.47 1.246 2 DAD747 3 3.0971.356 2 (1)Alcosperse 747 carboxylate band around 1565 cm⁻¹(2)Measurements taken after 20 water rinses, under dry nitrogen purge

TABLE 7.3 “C” Water uptake in PEC layer Formulation # (mAU) R DAD747 11.31 0.6 DAD747 3 1.70 2 DAD747 2 1.73 2

Table 7.3 shows results of FT-IR analysis of the water uptake of thecompositions of Table 7.1, demonstrating that hydrophilic thin layerscan be produced from formulations containing these oxidant-stableassociative PECs. By controlling the composition of the associative PECsand the exposure conditions, hydrophilic modification of surfaces can beaccomplished in one embodiment of the present invention by usingtreatment compositions that can contain oxidants for simultaneousdisinfection and cleaning of surfaces to which the inventivecompositions are applied.

Example 8

The associative PECs of the present invention can be used to incorporateantimicrobial molecules into the thin, invisible layers formed on avariety of surfaces exposed to treatment compositions, exhibitingenhanced substantivity of the biocides when they are incorporated intothe PECs layers, thus being available to reduce or eliminate germs onsurfaces that are subjected even to extensive rinsing with water, orexposure to high humidity, bodily fluids, etc.

When formulating associative PECs compositions that are to contain acharged surfactant or cationic biocide, or a mixture of a chargedsurfactant or biocide and uncharged surfactant, for example, it ispreferred to first assemble the associative PECs according to themethods of the present invention prior to introducing the chargedadjuncts.

TABLE 8 Federal Labs Alcosperse Glucopon Total Chitosan 465 PAA. 10 wt %Glucopon 325N/Barquat concentration Stock A Stock B Citric Acid H₂O 325Nstock 4250Z stock Charged groups Formulation # R (mL) (1) (mL) (2) (mL)(3) (mL) (mL) (mL) (mM) CPAA 11 0.25 7.2 9.7 20.6 258 10 0 1.32 CPAA 120.25 7.2 9.7 20.6 258 0 10.0 1.32 CPAA 13 0.5 12 8.23 18.5 257.60 0 10.01.34 CPAA 14 1.00 18.14 6.23 15.85 256.14 0 10.0 1.35 CPAA 15 1.5 21.764.98 14.2 265.4 0 10.0 1.30 CPAA 16 4 29.0 2.49 11.02 253.75 0 10.0 1.35(1) Chitosan stock 2.35 mg/mL, diluted into citric acid solution, orderof addition as required for given R value. (2) PAA stock 2.00 mg/mL,diluted into citric acid solution (3) Providing final 0.75 wt % citricacid at pH 2.2.

To demonstrate that formulations described in Table 8 containingquaternary ammonium biocide and nonionic surfactant are useful forcleaning and disinfecting surfaces, 10 microliters of each formulationwas applied to the Ge surface of the IRE and allowed to dry, followed by50 rinses with water, dried under dry nitrogen purge and then thespectra obtained with results shown in Table 8.1 below.

TABLE 8.1 Total Glucopon Barquat Citric concentration 325N 4250Z acidcharged groups Formulation # (wt %) (wt %) (wt %) (mM) R BIO1 (1) 0.0750.04 0.75 0 — BIO2 (1) 0 0.50 0 0 — CPAA 11 0.0739 0 0.75 1.32 0.25 CPAA12 0.0739 0.0394 0.75 1.32 0.25 CPAA 13 0.0737 0.0393 0.75 1.34 0.50CPAA 14 0.0737 0.0393 0.75 1.35 1.0 CPAA 15 0.0713 0.0381 0.75 1.30 1.5CPAA 16 0.0737 0.0393 0.75 1.35 4.0 (1) Controls with No PECs present.NA = Not Applicable.

Measurement of the quaternary ammonium biocidc (“Quat”) absorbance bandnear 2926 cm⁻¹ confirms it being present in the invisible PECs layersformed on the surface after treatment, despite the high number ofsubsequent water rinses. In contrast, monitoring of the absorbancc bandsattributed to the polysaccharide surfactant (APG) showed that thisneutral surfactant was completely rinsed away.

TABLE 8.2 Chitosan/PAA PECS exhibiting controlled quaternary biocideretention “A” “B” “C” CH₂ PAA Chitosan Water # Total C═O C—O uptake inQuat Rinses Quat band, band PEC layer presence Formulation # (1) (mAU)(mAU) (mAU) (mAU) (2) confirmed BIO1 10 2.328 0.439 0.395 −0.38 Y BIO250 1.555 0.288 0.435 0.05 Y CPAA 11 50 0.455 1.311 2.821 1.799 N (3)CPAA 12 50 1.644 0.724 1.46 0.638 Y CPAA 13 50 1.082 0.597 1.827 0.563 YCPAA 14 50 0.901 0.55 1.764 0.876 Y CPAA 15 50 0.833 0.4 1.923 0.883 YCPAA 16 50 0.365 0.336 2.534 1.271 N (3) (1) After surface treated withformulation (2) “C” = “A” − “B” (3) Absent or below detection limit

The data in Table 8.2 demonstrate that thin, invisible layersincorporating chitosan, PAA and the quaternary ammonium biocide areformed that resist extensive rinsing with water. It is believed, withoutbeing bound by theory, that adsorption of the Barquat onto the surfaceincreases the hydrophobicity (increases the water contact angle) due tonearly complete coverage of the surface and the orientation of thehydrophobic methylene chains of the Barquat molecules on the surface.The water uptake of the surface is significantly inhibited by thepresence of the adsorbed Barquat. Accordingly, the composition and Rvalue may be adjusted to provide the desired balance ofhydrophilicity/hydrophobicity and the desired level of an antimicrobialpresent in the deposited associative PECs layers. This is furtherillustrated in Table 8.2 showing that adjustment of the R value of theassociative PEC compositions can serve to change the amount ofquaternary biocide present in deposited films. Alternatively, the dataalso show how adjusting the R value is useful in adjusting the relativeamounts of chitosan and PAA present in the thin layers formed onsurfaces, and illustrates that at selected R values (0.25, 4) the higherlevels of chitosan present in the deposited associative PECs can beselected to control or prevent the retention of a similarly chargedquaternary biocide in the deposited layers. The presence of Barquatanchored to the surface treated with CPAA 16 is not detected, comparedto the case of the control sample BIO1, which does not contain PECs.Thus, composition CPAA 16 would be very useful in mitigating the loss ofBarquat to anionic sites on the surfaces of nonwoven wipes, cloths,mops, etc.

Example 9

In this example the effects of multiple applications of the inventiveformulations onto surfaces is illustrated using compositions shown inTable 9.1.

TABLE 9.1 Effect of multiple repeated treatments to surface “A” “B” “C”CH₂ PAA Chitosan Water Total C═O C—O uptake in Appli- Formu- Quat bandband PEC layer cation lation # (mAU) (mAU) (mAU) (mAU) R (Stepwise) BIO11.555 0.288 0.435 0.05 — 1 CPAA 12 1.233 0.679 1.565 0.515 0.25 1 CPAA12 1.332 0.961 2.195 1.02 0.25 2 CPAA 12 1.806 1.125 2.526 1.421 0.25 3CPAA 14 0.525 0.399 1.998 0.885 1.0 1 CPAA 14 0.532 0.479 2.664 1.4031.0 2 CPAA 14 0.619 0.434 2.715 1.446 1.0 3

Table 9.1 shows that the relative amounts of Quat and both polymers onthe surface increase with multiple stepwise applications of theinventive formulations, despite rinsing of the surfaces betweenapplications, and multiple exposures to the surfactants also present inthe formulations, demonstrating the durability of the associative PEClayers formed on the treated surface. Results also indicate that controlof the amount of adsorbed Quat is possible through selected of a desiredR value. The results also indicate that the water uptake of the layersdesirably increases with multiple exposures, yielding both hydrophilicmodification of the surface together with anchored biocide.

Example 10

In this example, the formation of an adsorbed layer of associative PECsonto a surface by employing a multi-step process is illustrated.

TABLE 10 Comparison of One and Two-Step Processes for FormingAssociative PEC Layers with Anchored Quaternary Ammonium Biocide “A” “B”“C” CH₂ PAA Chitosan Water Application Total C═O C—O uptake in Step #Formu- Quat band, band, PEC layer and Treatment lation # (mAU) (mAU)(mAU) (mAU) Detail (1) BIO1 1.555 0.288 0.435 0.05 Control (2) CPAA 110.536 1.511 3.093 2.31 Application 1 PECs without Quat BIO1 1.117 1.232.644 1.783 Application 2 Quat only CPAA 11 0.994 2.352 4.034 2.613Application 3 PECs without Quat BIO1 1.328 1.723 3.23 1.989 Application4 Quat only CPAA 12 1.233 0.679 1.565 0.515 Single Application PECs withQuat (1) All surfaces dried, then rinsed 50× with water after indicatedapplication step using specified formulation. (2) Quat alone, Barquat4250Z (0.5 wt %) present at same level as in “CPAA” series associativePECs treatments.

Results in Table 10 demonstrate that the non-inventive treatmentcomposition BIO1 results in the adsorption of some quaternary biocide onthe surface, but does not significantly increase the water uptake of thesurface, as indicated by the small “C” value. In contrast, treatmentusing inventive compositions with and without the quaternary ammoniumbiocide demonstrate the ability of the associative PECs formulations tonot only increase the surface hydrophilicity (indicated by the increasedwater uptake) but to deposit and hold a much greater level of the Quatbiocide with the invisible deposited PECs film on the treated surface.Surprisingly, once the associative PECs layer is formed on a treatedsurface, subsequent exposure to a biocide-only containing compositionresults in substantial uptake of the biocide into the PECs layer. Thus,the associative PECs may be employed in a two step process whereby anestablished PECs layer can be rendered antimicrobial by subsequentexposure to a biocide containing solution free of the associative PECs,without any significant removal of the originally deposited PECs layer.

These results demonstrate that the amount of quaternary ammonium biocideand the amount of deposited associative PECs on a treated surface can berenewed by individual applications of a biocide/surfactant formulationor an associative PECs treatment composition, with or without quaternarybiocide present. Thus, embodiments in which cleaning of the surface isdone first, followed by “touch up” applications of a cleaning and/ordisinfecting product without the associative PECs present is possible aswell. These compositions represent embodiments of the present inventionin which associative PEC treatment of a surface may be alternated and/orcombined with other surface treatment means.

Example 11

This example repeats similar treatment steps to Example 10 with theexception that the treated surfaces were not allowed to completely drybetween individual treatment steps in order to illustrate the durabilityof the associative PECs.

TABLE 11 Anchoring of Quaternary Ammonium Biocide With and Without PECLayer “A” “B” “C” CH₂ PAA Chitosan Water Total C═O C—O uptake in Formu-Quat band band PEC layer lation # (mAU) (mAU) (mAU) (mAU) Treatment (1)BIO2 1.632 0.265 0.402 0.224 Application 1 Biocide without PECs BIO21.717 0.36 0.457 0.721 Application 2 Biocide without PECs BIO2 1.8710.391 0.466 0.765 Application 3 Biocide without PECs CPAA11 0.668 1.862.679 1.636 Application 1 PECs without biocide BIO2 4.359 1.125 1.7731.1 Application 2 Biocide without PECs BIO2 3.419 1.278 1.77 1.276Application 2 (2) Biocide without PECs (1) Surfaces rinsed 50× withwater after indicated application step, without allowing time forindicated formulation application to dry on treated surface. (2) Same as(1) but rinsed 100× with water.

The results in Table 11 show that more quaternary biocide is anchoredonto the surface which has been first treated with the biocide-freeassociative PECs formulation than is anchored onto the surface which isinitially clean, but which has not been treated with the associativePECs formulations. Surprisingly, even three successive treatments of thesurface with a formulation having a relatively high concentration of thequaternary biocide alone does not result in as much anchored Quatbiocide as a single, two-step treatment in which a layer of biocide-freeassociative PECs is established, followed by “loading” of theestablished associative PECs layer by subsequent application of thebiocide only containing formulation (BIO2 formulation.). Thisillustrates utility of embodiments of the present invention employing atwo step modification of a surface that would be applicable for use incleaning a toilet bowl interior, for example. In one embodiment, thesecond treatment step could be used to introduce an antimicrobial agentafter an initial cleaning step that establishes the associative PECslayers onto treated surfaces. In another embodiment of the presentinvention, the renewal of the quaternary ammonium biocide in anassociative PECs layer can be accomplished by delivery, for exampleusing a toilet rim hanger device or in-tank device, of a sufficientamount of quaternary ammonium biocide to the bowl with each flush.

Light Scattering Measurements of PECs Solutions

Light scattering techniques are used to characterize the absolutemolecular weights as well as the size of the associative PECs of thepresent invention. Dynamic light scattering experiments are used todetermine the hydrodynamic radii (R_(H)) of the associative PECs, whilestatic light experiments are used to measure the absolute molecularweight (MW) and radii of gyration (R_(G)) of the associative PECs. Thoseskilled in the art recognize that R_(H) and R_(G) can have somewhatdifferent absolute values, and that their ratio (p=R_(G)/R_(H)) can alsoprovide information on the shape of the colloidal particles. Low valuesof p are observed for particles that are spherical, intermediate valuesare found for particles which can dynamically assume shapes that areslightly elongated, while the higher values are observed for particlesthat are more rigid and formally rod-shaped in aqueous solutions.

The hydrodynamic radii (R_(H)) of the associative PECs of the presentinvention were obtained via dynamic light scattering experiments thatemployed a Wyatt DynaPro DLS detection system with a 50 mW laser(wavelength=830 nm). Fluctuations in light scattering intensities wereobtained at 90° and autocorrelation functions were derived usingDYNAMICS software provided by Wyatt Technology Corporation. Allexperiments were conducted under controlled temperature and humidity anda total of 100 acquisitions were collected for each sample. Prior toanalysis by DLS, each associative PEC sample was centrifuged for onehour at 3750 rpm to remove dust.

Radii of gyration (R_(G)) and the weight-averaged MWs (M_(w)) of theassociative PECs were measured by batch-mode static light scatteringusing a Wyatt DAWN-EOS multiangle laser light scattering (MALLS)detector (wavelength=690 nm). Prior to analysis, the system wascalibrated at 90° with toluene and the other detectors were normalizedusing a 56 kDa PEO standard dissolved in a 0.7 wt % citric acid. Sampleswere centrifuged at 3750 rpm and immediately analyzed incustom-engineered light scattering cuvettes (Wilmad-Labglass). Debyeplots were generated for each sample, which yielded both R_(G) andM_(w). All light scattering data was processed in ASTRA V software usingeither first or second-ordered fitting.

Example 12 Controlled Particle Size of Chitosan/PAA PECs

Results in Table 12 are presented from light scattering analysis of theassociative PECs formulations described in Table 1B.

TABLE 12 Molecular Weights and Radii of Stable Chitosan/PAA PECsDetermined Via Light Scattering Molecular Weight R_(G) R_(H) Formulation# R (Daltons, ×10⁵) (nm) (nm) CPAA 1 0.25 35.4 47.4 97.6 CPAA 2 0.5021.1 45.8 88.8 CPAA 3 0.75 17.6 42.3 88.2 CPAA 4 1.00 17.9 40.40 90.7CPAA 5 1.26 10.3 67.50 60.55 CPAA 6 1.49 9.38 63.00 56 CPAA 7 1.76 9.3363.50 57.65 CPAA 8 2.01 7.35 56.10 49.55 CPAA 9 3.00 5.72 60.90 42.25CPAA 10 4.04 4.66 64.60 38.15

Measurements indicate that stable associative PECs with R_(G) less thanor equal to 300 nm (corresponding to diameters less than about 600 nm)can be produced via the inventive processes described herein, over arange of R values.

Example 13 Chitosan/PAA PECs Containing Antimicrobial Metal Ions

Many metal and transition metal cations, such as silver ions, are wellknown to the art to exhibit anti-microbial activity. In one embodimentemploying the associative PECs of the present invention, associativePECs may be used to anchor silver ions onto surfaces, through treatmentof the surface with associative PECs containing silver ions, oralternatively employing a two-step treatment process similar to thatdescribed in Examples 10 and 11. The ability of associative PECs tomodify surfaces, as described hereinabove, can be thus be used to easilyprovide a wide variety of treated surfaces exhibiting residualantimicrobial activity afforded via silver (or other germicidal metalions), in product executions in which quaternary ammonium biocides arenot preferred, for aesthetic or safety reasons, or in the case ofproducts perceived as more “natural” or “sustainable” by consumers, inwhich a biocide which is produced from non-petrochemical materials isdesired.

Exemplary associative PECs decorated with silver ions (Ag⁺) areassembled using the initial steps of the process described for theproduction of the formulations summarized in Table 1B.

TABLE 13.1 Compositions of Chitosan/PAA PECs with Silver Ions AlcosperseTotal Chitosan 465 10 wt % Tinosan concentration Total Ag+ Formulation #Stock A Stock B Citric Acid SDC H₂O charged groups Ion (a) R (mL) (mL)(mL) (mL) (b) (mL) (mM) (ppm) CPAG 1 0.25  8.21 (1) 9.42 (2) 12.03 4.1267.21 1.29 29.9 CPAG 2 0.50 13.79 (1) 7.91 (2) 9.56 4.1 265.58 1.3030.1 CPAG 3 0.75 17.71 (1) 6.76 (2) 7.79 4.1 264.54 1.30 30.1 CPAG 41.00 20.65 (1) 5.95 (2) 6.53 4.1 263.69 1.31 30.1 CPAG 5 1.25 23.01 (2)5.27 (1) 5.46 4.1 263.05 1.30 30.0 CPAG 6 1.50 24.72 (2) 4.74 (1) 4.714.1 262.62 1.30 30.2 CPAG 7 1.75 26.22 (2) 4.31 (1) 4.07 4.1 262.18 1.3030.2 CPAG 8 2.01 27.48 (2) 3.93 (1) 3.48 4.1 261.83 1.30 30.3 CPAG 92.99 31.02 (2) 2.98 (1) 1.88 4.1 260.83 1.31 29.9 CPAG 10 4.00 32.90 (2)2.36 (1) 1.04 4.1 260.36 1.30 30.0 (X) Denotes order of addition, “1”being the minor component and “2” the major component. (a) Materials andstock solutions as described in Table 1A. (b) Source of Ag⁺ ions,obtained from Pure Biosciences, Inc.

The molecular weights and particle sizes of the associative PECs in thesolutions in Table 13.1 were determined as described above, resultingdata summarized in Table 13.2.

TABLE 13.2 Molecular Weights and Radii of Stable Chitosan/PAA PECsDecorated with Ag⁺ ions, Determined Via Light Scattering MolecularWeight R_(G) R_(H) Formulation # R (Daltons, ×10⁶) (nm) (nm) CPAG 1 0.2526.3 122.8 173.3 CPAG 2 0.5 20.8 134.8 221.3 CPAG 3 0.75 11.1 117.1205.6 CPAG 4 1 8.46 133.9 187.4 CPAG 5 1.25 4.59 98.5 159.5 CPAG 6 1.54.88 114.1 188.4 CPAG 7 1.75 6.76 111.7 249.4 CPAG 8 2 6.61 111.8 282.2CPAG 9 3 5.39 144.9 193 CPAG 10 4 4.84 145.8 214.5

Results in Table 13.2 indicate that stable associative PECs with R_(G)and or R_(H) less than 300 nm (corresponding to diameters less thanabout 600 nm) can be produced via the methods described herein, over awide range of R values. The data also indicate that the molecularweights of the associative PECs in solutions containing soluble Ag⁺ ionsare significantly larger than in the case of associative PECs of similarcomposition made in the absence of Ag⁺ ions, indicating significantuptake and/or association of the silver ions with the associative PECswithout inducing displacement of the cationic chitosan component orphase separation or precipitation in the inventive treatments, which allremained clear and stable, and produced thin invisible films on treatedglass surfaces.

Example 14 Concentration Ranges for Production of Stable Chitosan/PAAPECs Formed Near R=1.0

This example illustrates associative PECs prepared using a differentchitosan source were the amount of PAA (poly(acrylic acid)) was fixedbut with varying molecular weights of PAA compared. Surprisingly, stableChitosan/PAA PECs with compositions corresponding to values of R=1.0 canbe made according to the methods of the present invention by selectingthe appropriate order of addition of the polymers and usingconcentrations of the polymer stock solutions that are not excessivelyhigh, for example, in one embodiment where the total combinedconcentration of charged groups on the associative PECs polymers arebelow about 25 mM.

TABLE 14.1 Total Total Stable Chitosan PAA 10 wt % final concentrationand Clear R Stock Stock Citric Acid H₂O volume charged groups Solution(1) (mL) (2) (mL) (3) (mL) (4) (mL) (mL) (mM) Obtained? 1.05 0.43980.1459 1.2114 16.7363 18.5334 0.53 yes 1.06 2.0749 0.6811 0.5491 15.303918.6090 2.49 yes 1.04 5.0044 1.674 — 11.8330 18.5114 6.10 yes 1.038.0199 2.7068 — 7.8212 18.5479 9.81 yes 1.04 12.0289 4.0102 — 2.502718.5418 14.63 yes 1.03 14.0127 4.7177 — — 18.7304 16.95 yes (1) Allcompositions 16.95 mM final concentration in terms of the total chargedgroups present. (2) 0.2 wt % Univar chitosan, Pharma grade, lotWA200701010), average MW or 1.0 × 105 Daltons (3) 0.235 wt % Alcosperse465 (Alco Chemical), average MW 8.0 × 10³ Daltons. (4) 0.7 wt % finalcitrate level in all compositions.

Associative PECs formulations described in Table 14.2 were made in thesame manner as described for those in Table 14.1 and indicate thatstable associative PECs may be assembled using the methods of thepresent invention to yielding Chitosan/PAA PECs with R values very closeto 1.

TABLE 14.2 Total Total Stable Chitosan PAA 10 wt % final concentrationand Clear R Stock Stock Citric Acid H₂O volume charged groups Solution(1) (mL) (mL) (mL) (mL) (mL) (mM) Obtained? 1.06 0.4522 0.3724 1.196216.5387 18.5595 1.37 yes 1.05 2.0206 1.6786 0.5364 14.2945 18.5301 6.14yes 1.03 5.0152 4.227 — 9.3048 18.5470 15.34 yes (1) All compositions15.34 mM final concentration in terms of the total charged groupspresent.

Example 15

The following embodiments of the present invention explore concentrationranges for production of stable Chitosan/PAA PECs using an alternativePAA source for values of R approaching 1.0.

TABLE 15.1 Total Total Stable Chitosan PAA 10 wt % final concentrationand Clear Stock Stock Citric Acid H₂O volume charged groups Solution R(mL) (1) (mL) (2) (mL) (mL) (mL) (mM) Obtained? 1.06 0.4522 0.37241.1962 16.5387 18.5595 1.37 yes 1.05 2.0206 1.6786 0.5364 14.294518.5301 6.14 yes 1.03 5.0152 4.227 0.0000 9.3048 18.5470 15.34 yes 1.048.0262 6.7122 0.0000 3.8109 18.5493 24.45 yes 1.04 10.0828 8.4495 0.00000.0000 18.5323 30.78 yes (1) 0.5 wt % Univar chitosan (2) 0.235 wt %Aquatreat AR-7H (Alco Chemical). average MW 8.7 × 10⁵ Daltons

The Chitosan/PAA PECs were assembled using the same procedure as inExample 13. Results in Table 15.1 indicate that stable associative PECsmay be assembled with the process and stocks described, yielding asolution of Chitosan/PAA PECs that had a final concentration, in termsof the total charged groups present of at least 30.78 mM.

Example 16 PECs Comprising Two Natural Polymers

Associative PECs containing two natural polymers, such as chitosanderived from crustacean shells, and alginic acid, may be used for theformation of natural polymer derived associative PECs. Further, use ofnatural or naturally-derived surfactants produced from sustainable,non-petrochemical feedstocks enable completely natural associative PECscompositions to be made. Reducing the environmental impact of householdproducts through the use of materials produced in a natural and/or moresustainable manner is of great interest to a significant number ofconsumers today.

TABLE 16 Compositions of Chitosan/Alginate PECs with and withoutNonionic Surfactant Sodium Total Chitosan Alginate, Glucoponconcentration Stock A Stock B H₂O Stock charged groups Formulation # R(g) (a) (g) (b) (g) (g) (c) (mM) CAL 1 0.10 0.23 (1)  2.4 (2) 16.38 1.01.50 CAL 2 5.0 2.05 (2) 0.44 (1) 17.51 — 1.52 CAL 3 5.0 2.05 (2) 0.44(1) 16.52 1.0 1.52 CAL 4 10.0  2.2 (2) 0.24 (1) 17.56 — 1.50 CAL 5 10.0 2.2 (2) 0.24 (1) 16.57 1.0 1.50 (a) Stock A: 0.2 wt % chitosan (FederalLabs) and 0.7 wt % citric acid in deionized water (b) 0.2 wt % sodiumalginate from Sigma-Aldrich, # W201502 (from brown algae). (c) 1 wt %Glucopon 325N surfactant in deionized water. 1 min stirring. (1, 2)Order of addition: Polymer solution added (1) to deionized water or (2)to first polymer solution.

The modification of the Ge surface of an IRE using the inventiveassociative PEC formulations of Table 16 was investigated to illustratethat all natural Chitosan/Alginate PECs can be utilized in products suchas surface treatments or hard surface cleaners, which may or may not beallowed to dry on the treated surface.

TABLE 16.1 Characterization of Layers Formed With Chitosan/Alginate PECsAcid Chitosan “C” C═O Band Alginate and Alginate Water uptake Treatment(1) Alginic acid Carboxylate C—O Band in PEC layer Number of Formulation# (mAU) groups (mAU) (mAU) (mAU) Water Rinses CAL 1 1.55 1.40 3.86 3.496Dried, 50 CAL 1 1.39 1.31 3.67 3.316 100  CAL 2 0.24 0.545 1.885 0.78850 CAL 3 0.158 0.454 1.934 1.149 50 CAL 4 0.192 0.364 1.920 1.378 50 CAL4 0.192 0.403 1.980 1.458 50 (2) CAL 5 0.188 0.375 1.790 0.86 50 CAL 50.205 0.475 1.882 1.087 50 (2) (1) 5 minute absorption time withoutdrying unless otherwise noted, followed by number of rinses indicated.(2) CAL 4 and 5 formulations reapplied in a second application followedby addition rinses indicated

Results in Table 16.1 indicate that formulations both with and withoutsurfactant (here a naturally derived alkyl polysaccharide) are able todeliver significant hydrophilic modification to a treated surface evenwith relatively high surfactant concentration present. Results furtherindicate that these exemplary formulations deliver relatively rapidmodification of the surface in a “self-limiting” manner despite repeatedapplications, as was discussed in other examples above.

Dynamic Light Scattering Characterization of Chitosan/Alginate PECs

Dynamic light scattering (DLS) was used to measure the particle sizes ofsome Chitosan/Alginate PEC formulations. Those skilled in the art willrealize that it is sometimes possible via dynamic light scattering todetect the presence of more than one population of particles in amixture, especially when the average sizes of the populations are large,and the polydispersity of sizes of the populations is relatively small.The data in Table 16.2 indicate that the largest scattering particlespresent in the Chitosan/Alginate PECs formulations all exhibit averagehydrodynamic radii (R_(h)) less than 300 nm, consistent with thestability and clear appearance of the formulations. In the cases whereaverage radii could be calculated for two populations, it is believed,without being bound by theory, that peaks with the smallest R_(h) valuescould be due to soluble polymeric species incorporated into thesolutions that originate from the natural polymer raw materials.

TABLE 16.2 Dynamic Light Scattering of Chitosan/Alginate PECs Peak 1R_(h) Peak 2 R_(h) Formulation # R (nanometers) (nanometers) CAL 1 0.110  93 CAL 2 5.0 27 169 CAL 3 5.0 103 Not detected CAL 4 10.0 20 128 CAL5 10.0 18 132

Example 17 Atomic Force Microscopy Images of Layers Formed by PECs

Images of the layers formed by exposure of surfaces to stableassociative PECs can be obtained via atomic force microscopy (AFM). Theimages shown were obtained in Non-Contact “Tapping” Mode using a VeecoCP-II Atomic Force Microscope (AFM). AFM tips were Veeco RTESPA-CPmounted tips (1-10 Ohm-cm Phosphorus (n) doped Si) with a resonantfrequency approximately between 256-295 kHz, and a spring constantapproximately between 20-80 N/m. The resonant frequency for each tip wasdetermined experimentally and applied prior to image acquisition.Software used for image acquisition was a Veeco Digital Instrumentsmodel CP-II Proscan 1.8.

FisherFinest Premium Microscope Slides were exposed to the associativePECs formulations for five minutes, followed by rinsing with 250 mL ofhigh quality water provided by a Barnstead NanoPure system. Treated andrinsed slides were then dried in air protected from dust prior to AFMimaging.

Multiple images were collected per surface-treatment to substratecombination. For each image, Topography and Phase data were acquired inboth scan directions and compared for similarity. For example, eachimage in a horizontally acquired scan would have forward and reversetopography and phase data. Scan rate was set between 0.25-1 Hz. Scansizes ranged from 0.25 to 5 square microns. Set points were between−0.04 and −0.06 microns. Topography images acquired with Proscan 1.8were processed using Image Processing and Data Analysis, version 2.1.15,by TM Microscopes. Additional details on the practice of AFM can befound in “Noncontact Atomic Force Microscopy”, S. Morita, R.Wiesendanger, E. Meyer, Eds. Springer-Verlag: Berlin, Heidelberg, NewYork. 1^(st) Ed, 2002, incorporated herein by reference.

The AFM images of a layer formed on glass slides from exposure to aChitosan/PAA PEC formulation without added silver ions, with a Rparameter of 0.25 (formulation CPAA 1, Table 1B) and a layer formed onglass slides from exposure to a Chitosan/PAA PEC formulation (R=0.25)which contained silver ions (formulation CPAG 1, Table 13.1) wereobtained, the images shown in FIGS. 3 and 4. Table 17.1 summarizes thecharacterization of the images of the layers on glass formed fromexposure to these associative PECs formulations.

TABLE 17.1 Topographical Characteristics of AFM Images of PECs Layers onGlass Formulation Topographical Parameter CPAA 1 (1) CPAG 1 (2) Diameterof PEC particle (nm) 50-100 100-150 Height of PEC particle (nm) 10-15  25 (min and max range in nm) (7-17) (20-40) Number of particlesanalyzed 373 285 (1) See FIG. 3 image on glass substrate (2) See FIG. 4image on glass substrate

Results shown in FIGS. 3 and 4, and Table 17.1 indicate that the glasssurface exposed to the formulations followed by rinsing (i.e., no dryingstep of the formulation onto the glass) acquire a significant number ofassociative PEC particles. The particles appear to be roughly circularand of uniform dimension, having thicknesses significantly less thantheir diameters. Thus, the topography data suggest that the particlesare “pancake-like” in shape. The data also show that the associativePECs having silver ions present appear a bit larger. The “phase” imagesalso can be interpreted to mean that the mechanical properties(stiffness, resistance to flow) of the particles in the images are allvery similar, and are thus of very similar if not identical chemicalcomposition.

Example 18 Scanning Electron Microscopy—Electron Images of Layers ofPECs with Silver Ions

FIG. 5A shows a secondary electron image of a layer formed on glassthrough exposure to formulation CPAG1. The layer was prepared in thesame manner as that described in AFM image study, Example 17. Aparticular associative PEC particle was selected for elemental analysis,as indicated by the cursor location in the electron image labeled“spectrum 40”. The X-ray spectrum of this particular particle is alsoshown in FIG. 5B. Results support the presence of silver ions in theinvisible layers formed on glass from exposure to Chitosan/PAA PECtreatment compositions.

Example 19 PECs Formulation with Anionic Surfactant and Buffer System

The stability of the associative PECs taught herein is not believed tobe a function of the pH of the formulations, provided that the polymerscomprising the associative PECs are soluble in the stock solutions usedand the appropriate order of addition, with respect for a given desiredR value, is employed. It is possible to create stable associative PECsin formulations that contain significant amounts of buffering salts,which may be required for the chemical stability of other formulationingredients. As an example embodiment of a salt tolerant associativePECs formulation, DADMAC/PAA PECs were assembled in a concentratedborate buffer. The anionic surfactant, being charged, was added afterassembly of the associative PECs as shown in Table 18.1, resulting instable associative PECs formulations at pH 8 with high buffer levels andsurfactant present.

TABLE 18.1 Anionic Cationic Total SAS charge charge concen- Concen- fromfrom tration Formu- tration PAA DADMAC charged lation # R (wt %) (1)(mM) (2) (mM) (3) groups (mM) IB-6 0.25 0.132 1.22 0.298 1.52 (1) 3 wt %secondary alkane sulphonate surfactant (Hostapur SAS 30, from ClariantCorp.), pH 8 borate buffer. (2) Polymer stock solution of PAA (AquatreatAR-4) 10 mM concentration of anionic acid groups, 0.073 wt %. (3)PDADMAC (Floquat FL 4540, SNF Corp., 10 mM concentration of cationicgroups, 0.161 wt %)

Commercial Examples

Table 19 illustrates embodiments of the present invention employingcommercially available ingredients to form associative PECs treatmentcompositions having utility in cleaning and disinfection of commonhousehold and commercial surfaces, all providing hydrophilicmodification of the treated surfaces in addition to other benefitsenabled by the optional adjuncts present.

TABLE 19 Composition Ingredient A B C D E F G H I Glucopon 0.1 0.04 ®325N (APG) Barquat 4250Z ® 0.06 0.3 Chitosan 0.0047 0.019 0.02(Federal Labs) Alcosperse 0.0075 0.002 0.00735 465 ® (PAA) Citric acid0.75 0.75 0.40 1.25 0.075 Chitosan 0.0055 (Sigma-Aldrich) Glucopon 0.753.00 425N ® (APG) Tinosan SDC 0.0136 (silver dihydrogen citrate)Chitosan (Univar) 0.135 Aquatreat AR- 0.053 7H ® (PAA) Sodium alginate0.0025 Radia ® Easysurf 3.0 6781 (alkyl polypentoside) Aquatreat 0.00870.0071 0.0033 0.0039 AR-4 ® (PAA) Floquat 4540 ® 0.0048 0.0081 0.00720.0073 (PolyDADMAC) Hostapur SAS30 0.15 Boric acid 0.6 Potassiumcarbonate 1.64 Sodium hydroxide To To To 0.1 pH 8.0 pH 11.2 pH 11.2Sodium silicate 0.016 Ammonyx LO ® 0.04 1.0 Sodium 0.025 2.0hypochlorite Fragrance 0.02 0.10 0.15 0.10 0.10 0.02 0.1 0.1 Deionizedwater balance balance balance balance balance balance balance balancebalance Key: A = Disinfecting cleaner B = Disinfecting lotion for use onnonwoven substrate containing wood pulp C = Disinfecting cleaner withsilver ion antimicrobial D = Toilet Bowl Cleaner E = Natural HardSurface Cleaner F = Mild pH Daily Shower Cleaner G = Daily ShowerCleaner with Bleach H = Mildew Remover with Bleach I = Toilet BowlCleaner

While particular embodiments of the present invention have beendescribed with respect to compositions, methods of preparingcompositions and methods of use, it will be clear that the invention isnot limited to these illustrative embodiments only. Numerousmodifications, changes, variations, substitutions and equivalents willbe apparent to those skilled in the art without departing from thespirit and scope of the invention as described in the following claims.

1. A method of forming a treated article, comprising: a. applying atreatment composition to at least one surface of an article comprising asuitable substrate material; b. allowing said treatment composition todeposit at least one layer comprising a plurality of associativepolyelectrolyte complexes on said surface; c. removing said treatmentcomposition from said surface by means selected from allowing thesurface to drain, allowing the surface to dry, wiping the surface with awiping implement, rinsing the surface with water, and combinationsthereof; wherein said treatment composition comprises: (i) an aqueouscomposition comprising at least one associative polyelectrolyte complexformed by combining a water soluble cationic first polyelectrolyte; anda water soluble second polyelectrolyte bearing groups of opposite chargeto said first polyelectrolyte; wherein the one polyelectrolyte presentin molar excess is added in the form of a first aqueous solution duringa mixing step to a second aqueous solution comprising the oppositelycharged polyelectrolyte present in molar deficiency; wherein R, themolar ratio of charged groups present on said first polyelectrolyte tooppositely charged groups present on said second polyelectrolyte isbetween 0.10 to 20; and wherein said treatment composition furthercomprises: (ii) a buffering agent; (iii) optionally, a surfactant; (iv)optionally, a biocidal agent; and (v) optionally, an oxidant.
 2. Themethod according to claim 1, wherein said mixing step is accomplishedwithout high shear mixing by means of a low energy mixing means selectedfrom liquid-to-liquid addition, stirring, static mixing, paddle mixing,low-shear mixing, and combinations thereof; wherein said low energymixing is accomplished at temperatures between 10 to 45° C.
 3. Themethod according to claim 1, wherein said plurality of associativepolyelectrolyte complexes is formed at a concentration of less than orequal to about 100 millimolar with respect to the total concentration ofcharged associating groups present on said polyelectrolytes present insaid plurality of associative polyelectrolyte complexes.
 4. The methodaccording to claim 1, wherein said plurality of associativepolyelectrolyte complexes have an average aggregate size in solution ofless than about 500 nanometers.
 5. The method according to claim 4,wherein said plurality of associative polyelectrolyte complexes have anaverage R_(G) and average R_(H) value in solution of between about 20nanometers to about 300 nanometers.
 6. The method according to claim 1,wherein said cationic first polyelectrolyte and said secondpolyelectrolyte are not selected from the group consisting of syntheticblock copolymer, polymer fluorosurfactant derived from polymerization ofa fluorinated oxetane, cross-linked polyacrylic acid, silicone polymer,anionic latex, water-insoluble anionic polysaccharide containingglucoronic acid, amphoteric derivatives of chitin or chitosan, includingcarboxymethyl N-acetyl chitosan, and a combination of chitosan andcopolymers of acrylate and styrene monomers, and/or styrene derivatives,and/or combinations thereof.
 7. The method according to claim 1, whereinsaid layer formed on the surface of said article is non-permanent,invisible to the human eye, capable of sequestering moisture from theatmosphere, and is less than about 500 nanometers in thickness.
 8. Themethod according to claim 1, wherein said surfactant is selected fromthe group consisting of water soluble and/or water dispersible anionic,cationic, zwitterionic, nonionic or amphoteric surfactants.
 9. Themethod according to claim 1, wherein said biocidal agent is selectedfrom the group consisting of alcohols, chlorinated hydrocarbons,organometallics, halogen-releasing compounds, metallic salts, pine oil,organic sulfur compounds, iodine, compounds, antimicrobial metal cationsand/or antimicrobial metal cation-releasing compounds, chitosan,quaternary alkyl ammonium biocides, phenolics, germicidal oxidants,germicidal essential oils, germicidal botanical extracts,alpha-hydroxycarboxylic acids, and combinations thereof.
 11. The methodaccording to claim 1, wherein said oxidant is selected from the groupconsisting of hydrogen peroxide, an alkaline metal salt and/or alkalineearth metal salt of hypochlorous acid, hypochlorous acid, solubilizedchlorine, a source of free chlorine, solubilized chlorine dioxide,acidic sodium chlorite, an active chlorine generating compound, anactive oxygen generating compound, a chlorine-dioxide generatingcompound, solubilized ozone, sodium potassium peroxysulfate, sodiumperborate, and combinations thereof and wherein said firstpolyelectrolyte and said second polyelectrolyte are oxidant stablepolymers.
 12. The method according to claim 1, wherein said plurality ofassociative polyelectrolyte complexes does not form a gel phase ormacroscopic solid phase.
 13. The method according to claim 1, whereinsaid first polyelectrolyte and said second polyelectrolyte is completelysoluble in water at a level of at least 10 g in 100 ml of water at atemperature of 25° C.
 14. The method according to claim 1, wherein saidtreated article is treated in a second treatment step comprising thestep of applying to the surface of said article a disinfectingcomposition comprising a biocidal agent and optionally a cleaningadjunct; wherein said layer of said plurality of associativepolyelectrolyte complexes on said surface of said treated articlethereby incorporates a sufficient amount of said biocidal agent so as toprovide an effective amount of the biocidal agent on the surface duringsaid second treatment step.
 15. The method according to claim 14,wherein said biocidal agent is selected from the group consisting ofalcohols, chlorinated hydrocarbons, organometallics, halogen-releasingcompounds, metallic salts, pine oil, organic sulfur compounds, iodine,compounds, antimicrobial metal cations and/or antimicrobial metalcation-releasing compounds, chitosan, quaternary alkyl ammoniumbiocides, phenolics, germicidal oxidants, germicidal essential oils,germicidal botanical extracts, alpha-hydroxycarboxylic acids, andcombinations thereof.
 16. The method according to claim 1, wherein saidfirst and second polyelectrolytes are selected from the group consistingof natural and/or naturally-derived polymers.
 17. The method accordingto claim 16, wherein at least one of said first and secondpolyelectrolyte is selected from the group consisting of chitosans,alginates, cellulosics, guar gums; and derivatives thereof; andcombinations thereof.
 18. An aqueous treatment composition for treatingthe surface of an article, comprising: (i) an aqueous compositioncomprising at least one associative polyelectrolyte complex formed bycombining a water soluble cationic first polyelectrolyte; and a watersoluble second polyelectrolyte bearing groups of opposite charge to saidfirst polyelectrolyte; wherein the one polyelectrolyte present in molarexcess is added in the form of a first aqueous solution during a mixingstep to a second aqueous solution comprising the oppositely chargedpolyelectrolyte present in molar deficiency; wherein R, the molar ratioof charged groups present on said first polyelectrolyte to oppositelycharged groups present on said second polyelectrolyte is between 0.10 to20; wherein said treatment composition further comprises: (ii) abuffering agent; (iii) a surfactant; (iv) optionally, a biocidal agent;and (v) optionally, an oxidant.
 19. The treatment composition accordingto claim 18, wherein said cationic first polyelectrolyte comprises acationic polymer with at least one monomer having a permanent cationiccharge or capable of forming a cationic charge in solution uponprotonation; wherein said cationic polymer is selected from the groupconsisting of chitosan and derivatives thereof, cationic guar, cationichydroxypropyl guar, cationic starch, derivatives thereof, andcombinations thereof; wherein said at least one monomer having apermanent cationic charge is selected from the group consisting ofdiallyl dimethyl ammonium salts, quaternary ammonium salts ofsubstituted acrylamide, methacrylamide, acrylate and methacrylate,trimethyl-ammoniumethyl methacrylate, trimethylammoniumpropylmethacryl-amide, trimethylammoniumethyl methacrylate,trimethylammonium-propyl acrylamide, 2-vinyl N-alkyl quaternarypyridinium, 4-vinyl N-alkyl quaternary pyridinium,4-vinylbenzyltrialkylammonium, 2-vinyl piperidinium, 4-vinylpiperidinium, 3-alkyl 1-vinyl imidazolium, ionenes, and combinationsthereof; and wherein said monomer capable of forming a cationic chargein solution upon protonation is selected from the group consisting ofacrylamide, N,N-dimethylacrylamide, N,N di-isopropyl-acryalmide,N-vinylimidazole, N-vinylpyrrolidone, ethyleneimine,dimethylamino-hydroxypropyl diethylenetriamine, dimethylaminoethylmethacrylate, dimethyl-aminopropyl methacrylamide, dimethylaminoethylacrylate, dimethylaminopropyl acrylamide, 2-vinyl pyridine, 4-vinylpyridine, 2-vinyl piperidine, 4-vinylpiperi-dine, vinyl amine,diallylamine, methyldiallylamine, vinyl oxazolidone; vinylmethyoxazolidone, and vinyl caprolactam, derivatives thereof, andcombinations thereof.
 20. The treatment composition according to claim19, wherein said second polyelectrolyte comprises an anionic polymerwith a least one monomer having a permanent anionic charge or capable offorming an anionic charge in solution; wherein said anionic polymer isselected from the group consisting of alginates, xanthates, pectins,carrageenans, guar, carboxymethyl cellulose, scleroglucans, derivativesthereof, and combinations thereof; wherein said monomer having apermanent anionic charge or capable of forming an anionic charge insolution is selected from the group consisting of acrylic acid, alginicacid, maleic acid, methacrylic acid, ethacrylic acid, dimethylacrylicacid, maleic anhydride, succinic anhydride, vinylsulfonate, cyanoacrylicacid, methylenemalonic acid, vinylacetic acid, allylacetic acid,ethylidineacetic acid, propylidineacetic acid, crotonic acid, fumaricacid, itaconic acid, sorbic acid, angelic acid, cinnamic acid,styrylacrylic acid, citraconic acid, glutaconic acid, aconitic acid,phenylacrylic acid, acryloxypropionic acid, citraconic acid,vinylbenzoic acid, N-vinylsuccinamidic acid, mesaconic acid,methacroylalanine, acryloylhydroxyglycine, sulfoethyl methacrylate,sulfopropyl acrylate, sulfoethyl acrylate, styrenesulfonic acid,acrylamide methyl propane sulfonic acid,2-methacryloyloxymethane-1-sulfonic acid,3-methacryloyloxypropane-1-sulfonic acid, 3-(vinyloxy)propane-1-sulfonicacid, ethylenesulfonic acid, vinyl sulfuric acid, 4-vinylphenyl sulfuricacid, ethylene phosphonic acid, vinyl phosphoric acid, derivativestherefore, and combinations thereof.
 21. The treatment compositionaccording to claim 20, wherein said cationic first polyelectrolyte andsaid second polyelectrolyte are not selected from the group consistingof synthetic block copolymer, polymer fluorosurfactant derived frompolymerization of a fluorinated oxetane, cross-linked polyacrylic acid,a silicone polymer, anionic latex, water-insoluble anionicpolysaccharide containing glucoronic acid, amphoteric derivatives ofchitin or chitosan, including carboxymethyl N-acetyl chitosan, and acombination of chitosan and copolymers of acrylate and styrene monomers,and/or styrene derivatives, and/or combinations thereof.